CN106537131A

CN106537131A - Printed gas sensor

Info

Publication number: CN106537131A
Application number: CN201580040108.6A
Authority: CN
Inventors: J·R·斯泰特尔; V·帕德尔; M·W·芬德莱; M·T·卡特
Original assignee: Sensor's LLC
Current assignee: Sensor's LLC
Priority date: 2014-06-27
Filing date: 2015-06-26
Publication date: 2017-03-22
Also published as: WO2015200755A1; EP3161470A1

Abstract

A printed gas sensor is disclosed. The sensor may include a partially porous substrate, an electrode layer, an electrolyte layer, and an encapsulation layer. The electrode layer comprises one or more electrodes that are formed on one side of the porous substrate. The electrolyte layer is in electrolytic contact with the one or more electrodes. The encapsulation layer encapsulates the electrode layer and electrolyte layer thereby forming an integrated structure with the partially porous substrate.

Description

The gas sensor of printing

Related application

This application claims the U.S. Patent application No.14/317 that on June 27th, 2014 submits to, 222 priority, the U.S. Patent application No.14/317,222 is that the part of the U.S. Patent application No.13/740,327 that on January 14th, 2013 submits to is prolonged It is continuous, U.S. Patent application No.13/740,327 is the U.S. Patent application No.12/953 that on November 24th, 2010 submits to, 672 Division, by quote by the entire disclosure be incorporated to this text.

Technical field

Following disclosure relates generally to the gas sensor for printing, and particularly includes liquid, polymer, solid Or the gas sensor and its method of the printing of gel electrolyte.

Background technology

Electrochemical cell has been used to the detection of toxic gas since twentieth century seventies, for example, setting for basis The fixed position instrument for applying (such as building and parking lot) and the portable secured and inspection equipment for using in transit.For example See Stetter, J.R., " Instrumentation to Monitor Chemical Exposure in the Synfuel Industry, " U.S. government and industrial hygienist community yearbook, 11,225-269, (1984).As these sensors exist Degree of accuracy, selectivity, linear and power requirement under low detection level, in environmental monitoring application, these sensors can be Preferably.Even when to manufacture in a large number, in the case of no any electronic component, technical grade electrochemical cell can make to disappear Expense person spends each more than $ 25 and or even hundreds of dollar.This cost can significantly increase gas monitor and detector Cost, and the little cost-effective selection of manufacturer can be left for produce super cheap and high performance detector. For example, for sensing carbon monoxide and in the presence of can be to the excessive concentrations of the adventurous carbon monoxide of life or health (CO) The high-quality of triggering alarm, accurate device are presently available for many commercial Applications, but are devices which in great majority It is still too expensive used in family.

As a result, selecting to have the less expensive sensor of unusual low performance to meet a large amount of consumer products cost mesh Mark, which causes relatively low performance and for the safety needed for consumer and the sacrifice of health protection.With in electrochemical gas biography Significantly reduce in terms of the cost and size of sensor, by make extra consumer, medical science and the application of industry become available. The gas sensor of other prior arts can use liquid proton conductor, wherein using NAFION^TMLayer coating sensing electrode and right The outer surface of electrode.NAFION^TMUndergo to freeze at 0 DEG C, its obstruction is by NAFION^TMThe sensor of coating is at 0 DEG C and following At a temperature of work.Further, since the rapid draing of liquid electrolyte, the life-span of these sensors can be from change in about 6-12 month It is dynamic.Therefore, because liquid electrolyte evaporates, reveals and/or corrodes, sensor needs to safeguard.In addition, sensor can have showing The manufacturing cost of work and be relatively large, has big electrolyte or water container sometimes, and which makes these sensor integrations to the modern times Equipment or little personal monitor it is difficult.

The gas sensor of another kind of prior art is using by proton conductor, for a type of conduction of sensing electrode Metallic catalyst and the design for merging to the different types of conducting metal catalyst of electrode.This allows the sensing electrode point Solution gas is to produce proton and electronics, and this pair of electrode shows do not have activity to decomposition gas.The result be two electrodes it Between can be used in detect object gas Nernst potentials.However, being included lentamente by problem caused by such design energy The gas reaction for carrying out or the disturbing reaction occurred on one or the other electrode surface.Extraly, response signal can be Weak.Additionally, the Nernst potentials can be difficult for zero and calibration is restricted to about 59mV per decade in clean air (decade) concentration.Again, the Jing often preferably works under high-temperature can be made with the electrolyte or electrode stability of time difference The performance degradation of the potential gas sensor of work.

Therefore, competitive electrochemical sensor can spend less manufacturing in a large number and have high-performance and little chi Very little, which produces new chance to develop the detector that can be manufactured in a large number of low cost to enterprise, therefore makes high accuracy Detector (such as those monitor and detect carbon monoxide and protect the detector of personnel and property) considerably cheaper.Do not have in performance In the case of lossy, this cost reduces to reform and greatly use of the enlargement gas detector in following their application On the way, including family's carbon monoxide monitors, automobile air quality and constructure ventilation and control.In addition, new application will become Possible, which includes needing protecting cheaply or monitor large-area avoids the secure group of toxic gas (such as carbon monoxide) Knit, and wish the university of toxic gas level or scientific research/environmental organization in research large area.In addition, can be in a cellular telephone Using can also be little electrochemical sensor so that the global network of CO and other gas monitors is possibly realized.

Traditional porous composite electrode is by 10-40 weight % politef (PTFE) and 60-90 weight % catalyst groups Into.Traditional electrode has possible residue dispersion thing, surfactant and thickening agent.These residual components are chemically inert With electrochemicaUy inert.Near the fusing point of PTFE (typically 290-310C), these electrodes are made to solidify and/or sinter.This needs Print to the base material of porous PTFE that for example can sustain PTFE solidification temperatures.PTFE serves as adhesive with porous bed (bed) catalyst granules is fixed together in.It acts also as the hydrophobic part of composite bed electrode to provide for three-phase The appropriate environment on border.This three-phase boundary is required for gas phase current type sensor.

Although there may be the various devices and technology for detected gas, it is believed that do not have a people the present inventor it It is front to have made or using the embodiment of as described herein invention, its allow to realize here thin and small form factor and Inexpensive component is together with high-performance.

General introduction

In one embodiment, disclose the gas sensor of printing.The sensor can be included：At least local gas are more Hole or ventilative base material；Electrode layer, the wherein electrode layer are included in formed on the side of the porous substrate two or more Multiple electrodes, one of them is the electrode of at least Local Porous；The dielectric substrate of solid, liquid, gel or identity function, wherein The dielectric substrate and the electrode layer electrolytic contacts；And encapsulated layer, the wherein encapsulated layer encapsulates the electrode layer and its part or complete Portion's base material and dielectric substrate, are consequently formed the integrated morphology with porous substrate.

In another embodiment, the gas sensor of printing is disclosed, which can include：Porous substrate；Electrode layer, its In the electrode layer be included in two or more porous electrodes formed on the side of the porous substrate；Formed on the electrode layer Wicking layer；Solid, liquid or gel electrolyte layer, wherein two or more electrolysis of the dielectric substrate and this are contacted； And encapsulated layer, the wherein encapsulated layer encapsulates the electrode layer, wicking layer and dielectric substrate and is consequently formed with the integrated of porous substrate Structure.

In yet another embodiment, disclose the method for manufacturing the gas sensor of printing.The method includes using Two or more electrodes (one of them is the electrode of at least Local Porous) are printed to this at least locally by metallic catalyst ink On the side of porous substrate；Solidify the porous substrate；Optional encapsulated layer with capillary channel is bound to into the porous base Thus material encapsulates two or more porous electrodes and forms electrolyte container；By the capillary channel liquid or gel Electrolyte fills the electrolyte container；And seal the capillary channel.

In a further embodiment, replacement polymer of the Porous gas electrode comprising the aqueous discrete particles of replacement standard PTFE Component.In certain embodiments, replace standard PTFE granule with dry PTFE granules.In other examples, with poly- third Alkene or polyethylene particle replace standard PTFE granule.

Although present specification is drawn a conclusion with claims, the claims are particularly pointed out and are distinctly claimed The protection present invention, but it is believed that the description below by some embodiments for combining accompanying drawing is better understood with the present invention.In accompanying drawing In, similar element is represented with similar numeral through some width figures.

Brief Description Of Drawings

Fig. 1 describes the exemplary version of the sensor of printing with cross-sectional view.

The substrate layer of the sensor of the exemplary printing that Fig. 2A and 2B are shown in describing Fig. 1.

The encapsulated layer of the sensor of the exemplary printing that Fig. 3 A and 3B are shown in describing Fig. 1.

Fig. 4 describes the exemplary version of the sensor of printing with cross-sectional view.

The substrate layer of the sensor of the exemplary printing that Fig. 5 is shown in describing Fig. 4.

The base material and electrode layer of the sensor of the exemplary printing that Fig. 6 is shown in describing Fig. 4.

The encapsulated layer of the sensor of the exemplary printing that Fig. 7 is shown in describing Fig. 4.

Fig. 8 is described in the reaction of the exemplary electrochemical in Porous gas electrode.

The exemplary version of the gas sensor of Fig. 9 description printings.

The exemplary version of the gas sensor of Figure 10 description printings.

Figure 11 A describe the exploded view of the gas sensor of the printing of Fig. 9.

Figure 11 B describe the partial assembly drawing of the gas sensor of the printing of Fig. 9.

The exemplary version of the sensor layer of the gas sensor of Figure 12 description printings.

The exemplary version of the sensor layer of the gas sensor of Figure 13 description printings.

Figure 14 electrodes of the diagram description comprising dry PTFE granules and the response signal of the electrode comprising PTFE aqueous solutions.

Response signal of the electrode that Figure 15 diagram descriptions are formed by 5-7 μm of PPRO powder particle in terms of μ Amps.

Response signal of the electrode that Figure 16 diagram descriptions are formed by 2-4 μm of PE powder particle in terms of μ Amps.

Figure 17 diagram description results of the CO signals to polymer particle sizes.

Figure 18 diagrams description gas port size and sensor are to the relation between sensor consistency.

It is not intended to by any way using accompanying drawing as restricted, and envision can be with (the bag by the way of many other Include unnecessary those modes being described in the drawings) carry out various embodiments of the present invention.It is introduced and form book A part for application documents has illustrated several aspects of the invention, and serves the original for explaining the present invention together with description The effect of reason；However, understanding that this invention is not limited to shown accurate arrangement.

Describe in detail

The scope of the present invention should not be limited using the description below of some embodiments.Other features disclosed herein, Aspect and benefit are by description below (which is illustrative, for carrying out one of best pattern contemplated by the present invention) to ability Field technique personnel will become obvious.As will be, it is realized that all in the case where the present invention is not left, version described herein Other different and obvious aspects can be accommodated.Therefore, it should by accompanying drawing and description be considered as it is substantially illustrative rather than It is binding.

The embodiments described herein includes the gas sensor for printing, and which includes：Porous substrate；Electrode layer, the wherein electricity Pole layer is included in two or more electrodes formed on the side of the porous substrate；Liquid or gel electrolyte layer, wherein The dielectric substrate and this two or more electrolysis are contacted；And encapsulated layer, the wherein encapsulated layer encapsulates the electrode layer and electricity Solution matter layer is consequently formed the integrated morphology with porous substrate.Wide model can be detected and is measured using the gas sensor of printing The target gaseous component enclosed.Only by way of example, can use it to detect CO, H₂S、NO、NO₂、SO₂、O₃And can It is the related compound of the compound of electroxidation or electroreduction.For exemplary electrical oxidation or the compound of electroreduction, see Stetter,J.R.Sang-Do,Han and G.Korotchenkov,“Review of Electrochemical Hydrogen Sensor,”Chemical Reviews 109(3),2009,pp 1402-1433；Joseph R.Stetter and Jing Li,in Modern Topics in Chemical Sensing:Chapter 4,“Amperometric Gas Sensors-A Review,”Chemical Reviews,108(2),2008,pp 352-366；Chang,S.C.,Stetter, J.R.,Cha,C.S.,“Amperometric Gas Sensors”,Talanta,40,No.4,pp 461-467,(1993)。

Porous substrate is at least partly ventilative and with enough holes so as to allow gaseous sample to pass through and in work Make to react at electrode, the working electrode or sufficiently porous so as to allowing the sample diffusion to metal surface and react.One In individual exemplary, when using aqueous or hydrophilic ionic liquid at room temperature (RTIL) electrolyte, the perforated membrane is selected from thin Moisture film.In an alternative embodiment, when using hydrophobic organic bath (i.e. ionic liquid or more particularly RTIL, in master The salt of the liquid condition included by ion and short life ion pair) when, the perforated membrane is selected from oleophobic (oligophobic) film.This Can be measured by contact angle.In some preferred embodiments, the contact of the RTIL/ organic baths on selected film Angle is equal to or more than the contact angle (about 90 °) on selected film for water or sulphuric acid.Exemplary film can be hydrophobic or close Water.Exemplary porous are hydrophobic and oleophobic film includes PTFE (such as Porex^TMMuPor^TMAnd Saint-Gobain^TM's Zitex^TM), polypropylene (such as Pall^TMPolypropylene filter, Sterlitech^TMPolypropylene screen), Merlon is (for example Sterlitech^TMMerlon tracking etching (PCTE) film discoid filter) and PVDF (such as Millipore^TM's Immobilon^TM).The hydrophilic film of Exemplary porous includes polyether sulfone (such as Pall^TMPoly (ether sulfone) film), the modified PVC in surface The modified polypropylene in (for example with the PVC of ozone-induced glycerol polymerization) and surface (for example with the polypropylene of UV radiation).Also Can be by processing perforated membrane so that the perforated membrane is hydrophobic with cytop, with the surface of the derivative perforated membrane of silane so that should Surface hydrophobicity, or the surface treatment chemicals of the hydrophobicity or oleophobic property (oligophobicity) for selecting to have required level Matter, makes exemplary film.

The embodiment of the gas sensor of printing described herein can utilize electrolyte, such as with some contact angles RTIL or H₂SO₄.The scope of the contact angle for working allows to summarize with regard to which kind of type being selected based on the scope of contact angle RTIL or other electrolyte.These contact angles for the feasible gas sensor performance of film of the gas sensor of printing are Important.The contact angle of the exemplary RTIL electrolyte being listed below is each example of the 2 μ L drops on MuPor porous PTFEs The Contact-angle measurement result of property electrolyte.4M H₂SO₄With about 118 ° of contact angles, 1- hexyl -3- Methylimidazole .sDouble (trifluoros Methyl sulphonyl) imines (1-Hexyl-3-methylimidazolium bis (trifluoromethylsulfonyl) Imide) with about 99 ° of contact angles, 1- ethyl-3-methylimidazolesDouble (trifluoromethyl sulfonyl) imines are connect with about 106 ° Feeler, 1- butyl -3- Methylimidazole .sDouble (trifluoromethyl sulfonyl) imines have about 90 ° of contact angles, 1- ethyl -3- methyl ImidazolesEthyl sulfuric acid ester has about 113 ° of contact angles, 1- butyl -3- Methylimidazole .sTetrafluoroboric acid ester is contacted with about 139 ° Angle, 1- ethyl-3-methylimidazolesTetrafluoroboric acid ester has about 122 ° of contact angles, 1- butyl -1- crassitudesCdicynanmide With the contact angle between about 131 ° and 134 °, and 1- butyl -1- crassitudesDouble [(trifluoromethyl) sulfonyls] Imines has about 71 ° of contact angles.In some embodiments of the gas sensor of printing, it is desirable to have comprising with more than 115 ° The electrolyte of the RTIL of contact angle.This offer high-quality in the measurement of hydrogen sulfide and ozone is responded and shall be appropriate for other Gasmetry chemical substance.

In an exemplary embodiment, base material is porous PTFE (such as trade name Zitex^TM、Gortex^TMOr MuPor^TM) and apply electrode matel material as black composite to make porous gas diffusive electrode.Additionally, the porous or Local Porous base material can include porous polymeric materials, for example porous Teflon, porous polyethylene, porous polypropylene, many Hole polyisobutylene, porous polyester, cellular polyurethane, porous polypropylene acids, porous flouropolymer, porous cellulosic polymeric, Can process to change porous fibre glass, the non-reacted thermoplastic of any other porous of hydrophobicity or oleophobic property with Jing Or its composite or mixture.In some embodiments, the porous or Local Porous base material are non-wettable.This is more Hole base material thickness can typically from about 100 microns to 250 microns change and can include with diameter about 0.1 micron to Hole in the range of about 5 microns.The porous substrate can be any thickness and can have and produce appointing for appropriate porosity What bore dia.The porous substrate can be placed on backboard 220 or have the appropriate gas of the working electrode for allowing access into sensor On the carrier of the hole (see Fig. 5) of the controlled in size of body entrance.The thickness of this backboard or carrier/porous substrate can be 0.002 to 0.005 inch and can be comprising polyethylene terephthalate (PET), Merlon, polypropylene or such as Fig. 4 With other the suitable plastics shown in Fig. 5, but the acceptable any thickness for producing selected or required gas access. Can place two layer stackups, gluing or otherwise and keep located adjacent one another.In another embodiment, backboard enters The demand that oral pore hole provides the entrance of porous and avoids for separate and distinguishing porous or Local Porous base material.

Porous substrate can have the ingress port of the entrance for gaseous sample to be measured.Should be by the ingress port Size adjusting to allow gaseous sample to enter the sensor, but should not too big and supply that cause gaseous sample beyond electricity The reactivity of the capacity of pole or required scope.For example, the ingress port hole can be from about 0.003 inch diameter to about Change in the size range of 0.080 inch diameter.For relatively low concentration (the CO sensors of such as 1-10ppm) can need compared with Big hole, and for the sensor (such as the CO sensors of 0-10000ppm) of relative broad range can select less hole. The ingress port can also be it is larger or less and depending on gas to be detected, the scope of required sensor and (such as signal diffusion-limited receives reaction rate for the specifically configured and demand of sensing reaction and the sensor mechanism of response Other restrictions of the signal of restriction or total electrochemical sensor).Can by punching press, cut, cross cutting, drilling or other The illustrative processes known form ingress port.Ingress port can be single porous zone or hole or hole or hole or have Allow the set of the material of the breathability of analyte entrance.Ingress port can containing selectively allow for analyte pass through and Stop the reactive explosive of some unwanted interference.In operation, gaseous sample the ingress port can be entered and be worn with Jing The sometimes optional porous substrate crossed on electrode layer opposite side is to reach working electrode and to react.Additionally, gaseous sample can With through the ingress port.The ingress port can be the straight perforated holes as shown in accompanying drawing or be with or without obstacle or The crooked route of filtering material.This allows the gas access of analyte to working electrode electrolyte interface.

Ingress port can be covered with filter, the filter is attached to or adjacent base material is otherwise maintained at The position of ingress port.Only by way of example, the filter can include any material, and its shield electrode layer avoids suppressing Or hinder the direct exposure of granule or any other unwanted environment in target analytes (which is to be analyzed) origin.Only By way of example, the filter can also include can remove wind and dirt, by sensor electrolyte evaporation impact simultaneously And reduce any material of the impact of the fluctuation of gas sensor upward pressure and air agitation.Only by way of example, the filtration Device can also cause object gas (in this example comprising removing chaff interference (such as the hydrogen sulfide in CO gas sensors) In be CO) can unimpededly through any material to electrode layer.The example of filter can include porous Teflon (PTFE), the KMnO on carbon, the carbon cloth of dipping, aluminium oxide₄With with the reactive explosive of powder or form of composite and bending Path.Filter for NO can be included in the triethanolamine on silica support.To anticipate as those skilled in the art Know, there are other chemical substances and other that can develop the gas sensing for the selective filter based on soda acid Absorbing or reactivity and other chemical substances.For example, Cu- acetates, bicarbonate or similar alkalescence can be used Salt is made a return journey except sour gas such as H2S or SO2.For the removal of ammonia, the aluminum oxide base material of acid medium such as pickling can be used； However, this can remove alkaline gas.Medium should be disperseed so as to the situation of the gaseous sample stream in without prejudice to sensor Under efficiently remove gas.

Electrode layer includes two or more electrodes, can design two or more electrodes to provide high or low table Area carrys out coordination electrode-electrolyte interface and makes the electric current of sensor export the noise minimum for maximizing and making in sensor Change.Signal Analysis for the optimum of target analytes will be considering for signal, background, noise and interference.The electrode layer Potentially act as ventilated membrane and the physical boundary between electrolyte and gas is provided.This physics of working electrode for control Structure be important and this control by black preparation control and curing process providing.Can also by electrode material sputter or Physically or chemically deposit to the substrate layer, or make to be located at the neighbouring substrate layer.Can lead on the side of porous substrate Cross silk screen printing or ink jet printing to form electrode layer.The thickness of electrode layer can typically from about 100 nanometers to about 125 microns (0.005 inch or 5 Mills) change, but can be certainly any thickness for effectively making analyte response.Depending on ink system Agent and the screen mesh size for deposition composites, silk screen printing typically produce the layer of 0.001-0.005 inches.Show at one In example property embodiment, silk screen printing is attractive because it is fast efficient technique and can be in same Time Stamp Brush multiple electrode (i.e. for two or more electrodes required for sensor operations) and simultaneously multiple device is printed To big substrate regions.For silk screen printing material can be for electrode required for any scope material, its bag Include for the Pt granules of CO sensors and for H₂The Au granules of sensor and SWCNT (the single wall carbon for ozone sensor Nanotube).

Electrode layer only needs two electrodes but more than two electrode is possible.First electrode referred to as can sense or Working electrode and contact with object gas sample to be detected.Second electrode is properly termed as to electrode, auxiliary electrode, to reference (counter-reference) electrode or public electrode.When object gas to be detected are contacted with sensing electrode, in sensing electricity There is oxidation or reduction reaction at pole, with the corresponding reduction to occurring at electrode or oxidation reaction.

For example, in the case of CO gas sensor, can there is following oxidation/reduction reaction.Carbon monoxide It is oxidized as follows：

CO+H₂O→CO₂+2H⁺+2e^-

(1)

In corresponding reduction reaction, proton (hydrion) is migrated through proton-conductive electrolyte membrane can be with oxygen to them Following reaction to electrode：

2H⁺+2e^-+1/2O₂→H₂O

(2)

It can be desirable to including extra or the 3rd electrode of the potential with the constant or approximately constant through reaction.This The electrode of sample can be referred to as reference electrode and can work in terms of the potential for stablizing sensing electrode.Or, can to electrode To be non-polarised and serve as reference electrode.The sensor is connected dense as reacting gas to read with suitable electronic component The electric current measured of degree.If additionally, the electric current in sensor is sufficiently small so as to minimally relative to the size of sensor electrode Make to electrode polarization, then to use this pair of electrode as the reference electrode in triple electrode circuit.These suitable ministrys of electronics industry Part can include to exhaustive circuit such as electric current to electric pressure converter, permanent potential instrument, galvanostat and current mirror (mirror). Current sensor operation and circuit are also possible in some cases.

Electrode layer can typically comprise the metallic catalyst from about 60% to about 90%, from about 2% to about 40% it is poly- Compound (the Teflon granules of such as micron-scale), in containing less than about 10% optional adhesive, less than about 10% Optional surfactant and from the black preparation of one or more optional modifying agent of about 0% to about 10%.Design this to stick Mixture to be maintained in electrode and provide structure carrier the modifying agent can be change electrode property (for example wetting characteristicss or Porosity) additive.The metallic catalyst can be powder, and only by way of example can comprising Pt, Pd, Au, Ag, Ru, Rh, Ir, Co, Fe, Ni, C or other noble metals or reactive metal, and its alloy or mixture.The metallic catalyst It can be the catalyst for loading carbon.For example, the carbon carrier can be the carbon of nano-granular, the graphitic carbon of ball milling, single Pipe, Au nano-particle or any suitable carrier.The adhesive can aid in offer with appropriate for silk screen printing Viscosity and evaporate/be dried the black preparation of ratio, and/or play by ink keep to base material and in curing process with base material conjunction And thereby the function of coordination electrode property such as hydrophobicity, hydrophilic and/or porosity (amount and type).Suitable adhesive Example includes Nicrobraz-S (by the Wall Colmonoy company Ke get of the Madison sea thatch positioned at Michigan) or polyethylene The solution of alcohol (PVA).Other suitable adhesive include silicate or aluminate materials, or polymer such as ethyl cellulose. The surfactant potentially acts as the solution stabilizer for black composite and can include solvent such as water, triton- 100th, Carbopol (carbopol) or other materials.The modifying agent includes a small amount of additive, and which processing and can solidify it Before, among and/or afterwards active control ink behavior.Suitable modifying agent can include polyvinyl alcohol, 1- propanol, Arabic tree Glue, n- sodium lauryl sulphates, ethanol or composite.Should in curing process in the material used in ink composition Normally evaporated by the combination electrode or roasting fallen, or the material should be electrochemicaUy inert and by the way of intentional not Change electrode performance, porosity or wettability.Using the material in ink composition generally should stay for electrolyte and Porosity, chemical composition, density and hydrophobicity or hydrophilic electrode required for the optimum interaction of analyte gas is urged Agent.In view of relevant control here is used for the teaching of the appropriate chemical and physical features of the electrode of gas sensing, for this Other suitable components of black preparation will be will be apparent for one of ordinary skill in the art.

Electrode layer and dielectric substrate electrolytic contacts.The dielectric substrate can be can provide for sensing and back reaction and with electricity Any suitable material of the electrolysis system required for the interface of pole.Suitable electrolyte includes the Aquo System of acid, alkali and salt And polymer dielectric such as Nafion, or non-aqueous system such as propylene carbonate lithium perchlorate, poly(ethylene oxide) lithium chloride Or ionic liquid.Electrode layer can with measurement apparatus (such as permanent potential instrument circuit) telecommunication.Telecommunication can be included to be had The track silk screen being printed directly on base material (two or more electrodes is for example connected to the stream of the printing of permanent potential instrument circuit Road and conductive trace) electrode layer.Electrode layer can be connected to outside gas sensor by permanent potential instrument electricity by the track Road.Telecommunication can also be comprising the wire connection extended by gas sensor to permanent potential instrument circuit by electrode.

In some embodiments, the electrode connects through the path of sealing to any material stream by the work in sensor Sensing active region at electrode is extended to outside sensor.Such construction is minimized and/or is eliminated through the sealing transmission Any kind of electrolyte, ion, gas, liquid or solid.The runner of printing can flow through comprising electronics but material can not The conductor (such as conductive trace with conductive ink) for enough flowing through.The conductor part of printing runner can include noble metal Solid line or belt.For example, the runner of printing can include the pressure-sensitive adhesive agent (PSA) with conductor part.Exemplary is expensive Metal includes but is not limited to Pt, Au, Ru or Ir.In some embodiments, the runner of printing is comprising non-porous and with regard to electricity The non-wettable carbon flow road of solution matter.The runner of printing includes polymer adhesive, and which can be the polymer (welded of welding Polymer), PSA or another kind of thermosettings or UV solidfied materials is inert polymer with regard to the element that accommodates in sensor Adhesive.Adhesive is sealed to the carbon flow road of electronics conduction.Sensor is needed within the life-span of the sensor to maintain this to seal, The life-span can be the several months to many decades.

Dielectric substrate can be liquid or gel or solid or composite and two or more electricity with electrode layer Pole electrolytic contacts.In some embodiments, (core includes two or more combinations for example to impregnate core by impregnated electrode layer To the electrode of core) dielectric substrate and electrode layer form electrolytic contacts.Only by way of example, dielectric substrate can include phosphorus Acid, sulphuric acid, water-bearing phosphate, aqueous sulfuric acid, methanesulfonic acid, aqueous phosphatic, sulfate solution, potassium hydroxide, aqueous acetic acid Lithium perchlorate, the polyvinyl alcohol with sulphuric acid, polyacrylic acid, ionic gel electrolyte or ionic liquid in potassium, propylene carbonate Body.Dielectric substrate can deliver entity comprising any suitable electric charge, and the electric charge delivery entity will be also supported needed for sensor The electrochemical reaction wanted and unwanted reaction or condition are not produced.In view of teachings herein other suitable materials are to ability The those of ordinary skill in domain will be apparent.

The sensor Inner electrolysis matter layer of printing can have substantially uniform thickness, typically close to about 5 from about 1 Mill That (125 microns).Dielectric substrate can include matrix or gellant to prevent dry or during vibrations or use movements Or otherwise strengthen sensor properties.Dielectric substrate can cover in sensor at least part of sensing electrode region and right Electrode.That is, it is with electrode layer electrolytic contacts, generally via the electrolyte container formed at least part of electrode layer.Electrolysis Matter layer can cover whole electrode layer or dielectric substrate can be with the electrode layer of covering part.Electrode layer can include what is be adjacent Chamber is accommodating extra electrolyte or carrier material so as to strengthen life-span or other performances of the electrolyte.In some embodiment party In case, electrode layer and dielectric substrate at one cause to arrange one or more electrodes to promote the electrolyte in dielectric substrate And the electrolytic contacts between one or more electrodes.

Encapsulated layer encapsulates the electrode and dielectric substrate so as to form the integrated morphology with porous substrate.The encapsulated layer is basic It is upper to form the contained structure with porous substrate and limit the interior part comprising electrode and dielectric substrate, removed by the contained structure Do not have material to enter or leave by one or more inlet holes.Design one or more inlet holes to allow analysis Thing is movable into and out contained structure.The interior of sensor can be fled from without material (except by the gas of the gas inlet port) Portion.This includes electrode and electrolyte.Encapsulated layer can comprising polyimides, Merlon, polyethylene, polypropylene, polyisobutylene, Polyester, polyurethane, polyacrylic, fluoropolymer, cellulosic polymer, fibrous glass, politef, any other is non-anti- Answering property thermoplastic.Encapsulated layer can also include embedding (potting) compound, can be suitable for reference to form encapsulation Other materials or its mixture or composite.In view of teachings herein, common skill of other suitable materials to this area Art personnel will be apparent.Encapsulated layer can be with the substantially uniform thickness from about 0.002 to 0.015 inch (2-15 Mills) Any size for substantially encapsulating of degree or permission sensor.The essence and its placement of the thickness and encapsulation is depending on sensor Size, the design of sensor and the technique used in assembling.

Encapsulated layer can also be included for into the capillary channel in dielectric substrate.It is such to be designed to accelerate electrolyte Filling and sensor are assembled.Encapsulated layer can also include gas discharge hole hole, its permission air when electrolyte fills the container Leave the electrolyte container.The gas discharge hole hole is can also allow on it there is big pressure oscillation such as aircraft or in submarine Gas detecting application in discharge.Only by way of example, it is possible to use plastic foil punching operation, cut or mould Cut to produce profile and/or hole to form capillary channel and gas discharge hole hole.Encapsulation should be formed and be not related to body of holding one's breath Entry design is entered with allowing analyte as discussed above.

The sensor of printing can also include the spacer body or absorber layer potentially acted as between electrode layer and dielectric substrate Wicking layer.It can also serve as and electrolyte is sucked sensor in process of production and electrolyte is kept against the material of electrode Material.By sandwich layer silk screen printing or can be ink-jet printing on all or part of electrode layer.Wicking layer can include silicate, carbon SiClx, carbon, graphite, aluminium oxide, fibrous glass, polymer can form other inert materials of multi-hole center.Biography here In sensor, wicking layer can be able to be still to allow core with the substantially uniform or variable thickness from about 5 to 125 microns Inhale functional any suitable thickness of layer.In some embodiments, electrolyte can impregnate sandwich layer with promote one or Electrolytic contacts between multiple electrodes and electrolyte.In some embodiments, the gas sensor of printing does not include wicking layer And one or more electrodes are directly screen printed onto on porous substrate.

In some embodiments, but core is not conductive is formed between electrode when being filled with ionic conductivity electrolyte Ionic conduction connection.When reacting at the electrode, the electricity produced in electrochemical reaction is conducted by electrolyte solution Son and ion.Electrolyte solution can be flowed freely or cover in core.Therefore, in this exemplary, The core is not ionic conduction, but the core has ionic conductivity plus the electrolyte structure in sensor.

In some embodiments, the gas sensor of printing is manufactured by following method：By two or more porous On the side of electrode print to porous or Local Porous base material, the porous substrate is solidified, and by the envelope with capillary channel Dress layer is bound to the porous substrate for encapsulating two or more electrodes and forming electrolyte container.By being used by capillary channel Electrolyte is filled electrolyte container and seals the capillary channel, and the method continues.In another embodiment, by following Method manufactures the gas sensor of the printing：Two or more porous electrodes are printed to porous or Local Porous base material On side, the porous substrate is solidified, electrolyte is printed or is placed in electrode zone, and and then encapsulated layer is bound to into this Porous substrate, thus encapsulates two or more electrodes with electrolyte and forms electrolyte container.The electrolyte is put at this Container is full.Electrode and the electrolysis of whole chamber are sealed by the gas inlet port with the unique channel for gas access Matter.In a further embodiment, electrolyte container can change for abnormal pressure with what is formed in the electrolyte container Become the steam vent of application.In each embodiment, electrolyte and electrode chambers become the causing except by the entrance of sealing This can be fled from using the gas sensor identical mode that printing is entered with analyte, no electrode or electrolyte in port Encapsulation.In each embodiment, the ingress port can be sealed.

The method can also comprising by politef, polyethylene, polypropylene, polyisobutylene, polyester, polyurethane, poly- third Olefin(e) acid class, fluoropolymer, cellulosic polymer, fibrous glass, its mixture or any other non-reacted thermoplasticity can be glued Knot polymer forms substrate layer.The base material can be formed by cut, cross cutting, punching press, roller mill or other film-forming process Layer.

The method can also comprising by politef, polyethylene, polypropylene, polyisobutylene, polyester, polyurethane, poly- third Olefin(e) acid class, fluoropolymer, cellulosic polymer, fibrous glass, its mixture or any other non-reacted thermoplastic polymer Or inert single or dual mixture epoxy type potting compound forms encapsulated layer.Molding, cut, mould can be passed through Cut, punching press or other suitable processing to be forming the encapsulated layer.

Using ink composition by the side of two or more electrode prints to porous substrate.As mentioned above, make Ink composition for the layer that prints electrode (i.e. two or more porous electrodes) can be included：From about 60% to about 90% urges Agent, from the polymer beads (such as the Teflon granules of micron-scale) of about 10% to about 50%, less than about 10% bonding Agent, less than about 10% surfactant and one or more modifying agent from about 0% to about 10%.The catalyst can be included Pt on the catalyst such as carbon or other carriers of noble metal such as Pt or Pd or alloy or load, because such preparation is in ability It is well-known in domain.Can be by silk screen printing, intaglio printing, ink jet printing, template spary or foundation teachings herein Other the suitable printing technologies known in the art that can be used are printed.In silk-screen printing technique, printing net can be with Comprising stainless steel silk, plastic grid or the platinum guaze lattice across screen frame.Depending on required printing film thickness and therefore printing Two or more electrodes thickness, size of mesh opening can change.Can make to treat silk using required electrode design template The region of wire mark brush is patterned on the net.Then ink can be spread all over into this using squeegee online and by required pattern Printing is on porous substrate.In ink-jet printing process, the formula of control ink is needed to cause ink to continue some times on the net at this Keep printable and be not dried too quickly.The blocker of addition should control this technique and an exemplary reality here The scheme of applying uses PVA/ aqueous solutions as the blocker or modified agent addition agent to metal-plastic ink composite-material formula.

The method can also include curing schedule, can be in the curing schedule by heating at about 100 DEG C -200 DEG C Or dry (such as lasting about 10 minutes in stove at 150 DEG C) comes cure sensor ink and porous substrate.Enter when using PTFE The solidification of one step can need extra to be heated to about 280 DEG C to 300 DEG C and last about one hour to be formed for gaseous reactive Proper settings and porous diffusion electrode.The solvent of any presence can be removed using the curing schedule.Passed by polluting Atmosphere around sensor component, the residual solvent not removed in this step process can cause problem.Can be for example, by strong System be air-dried (for example at elevated temperatures), infrared radiation, ultraviolet radiation, ion beam irradiation, gamma radiation and its Combination is solidified.Select curing schedule to repair the electrode structure in remaining compound porous or Local Porous electrode. It is used in the exemplary of CO, for example, continuing solidification PTFE granules (30%) in a hour and Pt at 300 DEG C at one The mixture of granule (60%) and ethyl cellulose (10%) is producing the tool of the measurement of 0.1-10000ppm CO in the air being used for There are the CO electrodes of available hole and hydrophilic/hydrophobic.Other electrode embodiments below will be described in further detail, including by The electrode that PFTE catalyst ink suspensions, the PTFE powder of drying, polypropylene powder or polyethylene powders are formed.Other are exemplary Electrode formulation includes the ink prepared plus 1.25wgt%PVA with 3.125wgt% ethyl celluloses.

The method can also include sandwich layer being printed to two or more electrodes and/or porous substrate.Can pass through The printing of wicking layer is completed using the black slurry silk screen printing comprising granular core material or ink jet printing.As mentioned above, The granular core material can comprising silicate, carborundum, carbon, graphite, fibrous glass, fibrous glass filter paper or other when being entangled in one Rise when formed hole or can wicking (wickable) base material porous material or fibrous material.In these embodiments, should Core material should not be conductive.Core ink can also comprising the filter paper based on silicon oxide, and which grinds or smashs into little particle to pieces and mix Conjunction has water or is added with the water of salt, acid or alkali.Said composition have sufficient water and medium (such as PVA, ethyl cellulose or Other blocker) make ink be suitable for printing.

In some embodiments, wicking layer can also include electrolyte such as salt (such as H₂SO₄), acid, alkali or class Like thing.The electrolyte can be drying material and can be activated into liquid by exposure to solvent (such as vapor) Electrolyte.Under without the conditions of demand for moist electrolyte addition, dry electrolyte can allow for be assembled Printing gas sensor such as drying baker in be dried.Any gas can be covered by removable adhesive such as paster Body entrance area (hole, porous zone or similar), avoids any gas with the gas sensor for sealing printing and enters.Work as electrolysis When material is exposed to air, the steam in air can enter the gas sensor of the printing and mix with electrolyte So as to the gas sensor of the printing is filled with liquid electrolyte.This can be completed by removing the removable adhesive, For example when in order that using and placing the gas sensor of the printing.

The combination of encapsulated layer or substrate layer can comprising thermal, chemical bond, adhesive combination, combination of ultrasound, lamination, Pressure is combined, o-ring is combined or is welded.Once encapsulated layer is bound to porous substrate is consequently formed electrolyte container, it is filled with Electrolyte container.Filling can be completed in electrolytic solution by the sensor of capillary channel or whole printing is immersed.Work as leaching When entering the sensor of capillary channel or printing, electrolytic solution is risen and is entered in the electrolytic vessel by the capillary channel.Once Inside container, the sandwich layer (if present) can be captured some electrolyte and it is held against electrode thus.In vessel filling Afterwards, the capillary channel and any aerofluxuss can be sealed for example, by heat seal, chemical seal, adhesive sealing (such as epoxy) Hole.When using core, need for air flow out steam vent and this should also be in end seal.This sealing can be filled Closure material is used for pressure gas porosity steam vent in a balanced way when sensor is used for pressure change application.

The gas sensor of the printing of generation can have various sizes and size.For example, the gas sensor of printing Thickness can be less than about 1000 microns (about 1mm).Filter layer is also included in the gas sensor of printing and container overflows layer In embodiment, the thickness is for about 3000 microns (about 3mm).Inventor constructs prototype sensor, wherein the total thickness of whole layers Degree is for about 500 microns thick.Current prototype has about 1mm²To about 9mm²Surface area and about 0.5mm to 1mm thickness.Because Continuously improve silk screen (silk screen) resolution, thus using the less sensor of approach described herein can be can Can.

The gas sensor performance of the exemplary CO electrodes for showing here can be with from about 0ppm to the CO of about 1000ppm Measurement range.In another example, the gas sensor performance for CO can be with from about 0ppm to about 500ppm's Measurement range.Measurement output signal from the CO electrodes of silk screen printing in the gas sensor can be from about 1 nanoampere/ppm Change to about 25 nanoamperes/ppm.Measurement output signal from the gas sensor can be with from about 10 nanoamperes/ppm to about 25 nanoamperes/ppm changes.It is that scope is selectable and be used for by selecting size these signals of gas inlet port The small hole of gas access can reduce these signals.Even more little signal (for example 10-100x is less) be it is possible simultaneously And can be amplified using available electronic machine at present.The gas sensor of printing is can occur in less than about 30 seconds at 20 DEG C Measurement response time.The gas sensor of printing can also produce the measurement response time of less than about 20 seconds at 20 DEG C.It is relatively thin Sensor can produce compared with fast-response time because reducing with shorter diffusion length diffusion time.For example, or even close 0%RH for a long time under conditions of, electrolyte volume here still produces highly stable sensor, so as to give this print The sensor of brush at the scene in use CO detections long-life.

In an exemplary for CO monitorings, the gas sensor of printing is using the electricity for being referred to as permanent potential instrument Electronic circuit carrys out electrochemically sense gasses.In permanent potential method or pattern, treat that the gas that quantitatively senses or detect can be Sensing electrode or working electrode are contacted in the presence of electrolyte and the electricity proportional to the amount of the object gas into battery is produced Stream.Public electrode can run complementary half-cell reaction to electrode.The reference electrode worked in permanent potential circuit can The thermodynamic electric potential of the working electrode is maintained during sensing.Can by simple electronic machine and sensor influence each other from And the electric current is changed to voltage and amplify the voltage for instrument or recorder reading.

Accompanying drawing is turned to, Fig. 1-3 describes the operable gas sensing for detecting and measuring the printing of carbon monoxide level The example of device.Certainly, in view of teachings herein, other mesh that can be detected using the gas sensor of the printing and/or be measured Gas body is will be apparent to one of ordinary skill in the art.In addition, although have been disclosed for exemplary geometry, but To be possible to one of ordinary skill in the art's others geometry.In addition, though having been disclosed for for exemplary The example combinations of the black property (viscosity, composition, dry rate etc.) and ink structure (thickness, porosity etc.) of sensor, but One of ordinary skill in the art can envision other ink and composition and property and structure.Although having been disclosed for using print The example combinations of these specially designed parts of dataller's skill and packaging technology, but material described herein is combined by this A series of new way of many special characteristics of material and technique, for the design and assembling of related electrochemical gas sensors Substitute will become obvious to those skilled in the art.

With reference now to Fig. 1, show the exemplary version of the gas sensor 100 of printing.The gas sensing of the printing of display Device 100 is included：Porous substrate 200, electrode layer 300, the liquid or gel electrolyte layer 400 with 300 electrolytic contacts of electrode layer, The gas that the printing with porous substrate 200 is consequently formed with the encapsulated layer 500 of encapsulated electrode layer 300 and dielectric substrate 400 is passed The integrated morphology of sensor 100.It should be appreciated that Fig. 1 is the schematic diagram of gas sensor 100 of printing and not pro rata.Example Such as, the no packed layer of dielectric substrate 300 500 separates.In some embodiments, encapsulated layer 500 is worn under and local advances The surface of porous substrate 200.In other embodiments, encapsulated layer 500 is sealed to electrode layer 300 to produce fluid-tight Envelope.During here is implemented, the substrate layer 200 is comprising porous Teflon (although can be in the region 205 for gas access Desirably using other porous materials with porosity) and print to porous PTFE base material 200 with showing Four electrodes on side.If using porous PTFE, adhesive or backboard (back-plate) can be used as long as or in institute The similar path of porosity is kept to carry out filling pore in the gas inlet area 205 of needs.Porous PTFE is for gas sensing But device electrode facilitates base material for printing can be difficult.The substrate layer 200 has to enter for gaseous sample to be measured The ingress port 205 for entering and the optional filter 215 for covering the ingress port 205 (can make substantially any shape and chi Sensor operations in the very little application with enhancing).Optional backboard 220 is illustrated in Figure 1 also.The backboard can include TFE base materials Or other plastics and the backboard can be utilized to block to whole base material 200 except opening corresponding to the ingress port 205 The gas access of mouth.Being not on scale this layer 220 and this layer 220 can be substantially very thin or only in layer Hole is filled in 200 completely or partly.

As also described in Figures 2 A and 2 B, show electrode layer 300 is with the test formed on the side of porous substrate 200 Electrode 310, reference electrode 320, work (or sensing) electrode 330 and to electrode 340, the side and gas access and optional filtration Device is relative.It should be appreciated that be similar to other components described herein or feature, if necessary to or sensing system need not, can be overall Omit test electrode 310 and reference electrode 320 in ground.The substrate layer 200 also describes the region 210 for treating to be encapsulated by encapsulated layer 500.Electricity Solution matter layer 400 is in the encapsulated layer 500 and and electrolytic contacts adjacent with the electrode layer 300.

The test electrode 310 can allow the gas sensor for printing self to test the deterioration or mistake of the working electrode 330 Effect (and therefore, the gas sensor 100 of printing senses the ability of simultaneously target gas concentration exactly) and recognize Sensor condition.The test electrode 310 can be arranged to sense the gas for generally existing in an atmosphere, such as oxygen detects electricity The decomposition of pole or electrolyte provides the temperature compensation capability or similar performance enhancement increased with the time.The examination can also be arranged Electrical verification pole 310 is producing the experimental gas in the sensor and with check amount implementing sensor (i.e. working electrode 330) Operation test.The test electrode 310 can include catalyst, its include Pt, Pd, Au, Ag, Ru, ruthenic oxide, Cr, Mn, Fe, Co, carbon, be suitable for sensor in need combination or alloy or the composite of summation function.For example pass in gas generation, electronics During sensor is tested or be similar, the test electrode 310 can also be electric pulse.

In this example, the working electrode 330 has sensing region 335 and comprising the platinum catalysis for CO sensings Agent composite, although the as disclosed above sensor that other metallic catalysts can be used to be used for CO or other gases. The reference electrode 320 can include Pt composites, Ag/AgCl, Pb/PbO2 or other be suitable for the material of sensor design. It is used in the particular example of CO sensors, using the black composites of Pt- at this.This pair of electrode 340 can include Pt, Au, Pb/ PbO2 or any is suitable for the material of the special sensor.In this special example, use and have Pt- black and Teflon The CO sensors of granules composite material.

Dielectric substrate 400 is with 300 electrolytic contacts of electrode layer and comprising the lithium perchlorate or replacement in propylene carbonate Polyvinyl alcohol with sulphuric acid or the sulphuric acid in cellular glass or aerated plastics matrix.The electrolyte can use ionic liquid Or solid polymer or at other electrolyte known to sensing system field (such as fuel cell and accumulator).The electrolyte Layer 400 covers the sensing region 335 of working electrode 330 and extends to other sensors electrode and causes whole electrodes in sensor (contacted by electrolyte) for electrolytic contacts.In some cases, for thin-film electrolyte and on electrode layer 300 or The contact of electrolyte container 410 that top is formed can also be required, and it can be formed in a part of encapsulated layer.Electricity Solution matter container 410 can be included when electrolyte container 410 is full of (such as when the volume of the electrolyte in high relative humidity conditions During expansion) with accommodate by 410 expansion of electrolyte container electrolyte expansion area 410A.

500 encapsulated electrode 300 of encapsulated layer and dielectric substrate 400 for such as showing in FIG is consequently formed with porous substrate 200 integrated morphology.As also described in figure 3 a, encapsulated layer 500 is comprising with the capillary channel 520 entered for dielectric substrate Capillary channel layer 510.Capillary channel layer 510 be further defined by from air accumulation moisture expansion process in electrolyte can Resident bucket volume 515.Capillary channel layer 510 is optional component for the operation of sensor.As described in figure 3b, encapsulate Layer 500 can also include the cap rock 530 with gas exhaust hole 540.For in one embodiment fill electrolyte and For using sensor and for the surrounding that senses changes the application of pressure with some speed, the gas vent is that have .Capillary channel layer 510 can also include that one or more permission electrolyte flow through the capillary channel of the capillary channel layer 510 Ingress port 510A.Profile and/or hole are produced by using plastic foil punching operation (in this example), cut or cross cutting Hole and the polypropylene that formed comes capillary channel layer 510 and cap rock 530 shown by cut.By two layer heat seals are existed Together or alternatively by adhesive combine two layers are bundled together, and and then by two-layer package heat seal or with Other modes are bound to porous matrix layers 200.Electrode or conductor is needed to expose by encapsulation so that producing with the electrode in being encapsulated in Raw outer contacting.Connection means can be：By wire, conductive plasticss, the runner of printing, the plastics of pre-metallization or conductor And can be sealed so that any material that can not be spilt by sensor in use for many years of electrode and electrolyte. Cap rock 530 also describes the region 535 of and sealing to be packaged using such as heat seal or PSA.Although showing that the encapsulated layer has two Individual sublayer, it should be appreciated that the encapsulated layer can have capillary channel, bucket volume and gas vent or at which comprising one The layer of any other optional feature of middle formation.Built-up time and cost that pre-formed these features should be saved in manufacture.

Fig. 4-7 describe it is operable for detect and measure the gas sensor of the printing of carbon monoxide level another Example.With reference to Fig. 4, the exemplary version of the gas sensor 1000 of printing is described.The gas sensor 1000 of the printing of display Carbon monoxide level can be measured；However, it is possible to use other object gas.Sensor 1000 is included：Porous substrate 1100, electricity Pole layer 1200, wicking layer 1300 contact and permeate the core 1300 and the liquid with 1200 electrolytic contacts of electrode layer or gel electricity Solution matter layer 1400, and encapsulate the encapsulated layer 1500 of the electrode layer 1200, wicking layer 1300 and dielectric substrate 1400 and be consequently formed tool There is the integrated morphology of porous substrate 1100.

As also described in Figure 5, although can use other porous substrates, but substrate layer 1100 comprising porous PTFE and With gas access hole 1105, in gas access, hole 1105 maintains the porosity of PTFE and by being bound to gas access The base material plastics of hole 1105 can completely cut off other all ground by additive of the brush on gas access hole 1105 is arbitrary Side.The substrate layer 1100 is also included in the filter 1115 of the blanketing gas inlet hole described in Fig. 4, and which can be for inciting somebody to action Plastic part of the porous PTFE by the environment isolation Anywhere in addition to the part of gas access.Notice the gas access Part is preferably alignd with the working electrode of the opposite side of printing to porous PTFE.In addition the base material 1100 for showing in figure 6 has Print to four electrodes thereon.Show electrode layer 1200 is with the test electricity formed on the side of the porous substrate 1100 Pole 1210, reference electrode 1220, work (or sensing) electrode 1230 and to electrode 1240.As mentioned above, if desired may be used Integrally to omit test electrode 1210 and reference electrode 1220.Substrate layer 1100 also describes to be packaged by encapsulated layer 1500 Region 1110.

In this example, although other metallic catalysts as disclosed above can be used, but working electrode 1230 has There is sensing region 1235 and comprising platinum metal catalyst.It is additionally operable to produce CO sensors in the special embodiment of here, to electricity Pole 1240 can include the black-PTFE porous electrodes composites of Pt.

The wicking layer 1300 of the sensor 1000 of display example printing in Fig. 4.Can be by 1300 silk screen printing of wicking layer Or be ink-jet printing on electrode layer 1200.Wicking layer 1300 can include silicate, Nafion, carborundum, carbon, graphite, fiber Glass filter paper, porous polypropylene and Teflon.Sandwich layer 1300 can also include and will will suck and keep electrolyte against sensing Other battery separator types of material of electrode in device；Such material with electrolyte compatible is selected typically.Here In embodiment, the core can not be conduction and can be wettable by selected electrolyte.

As described in the diagram, dielectric substrate 1400 is with 1200 electrolytic contacts of electrode layer and comprising in propylene carbonate The polyvinyl alcohol with sulphuric acid of lithium perchlorate or replacement, poly(ethylene oxide) and lithium chloride, ionic liquid, with some salt or The acetic acid of the hydroxide solution of KCl or sodium, potassium or caesium.The dielectric substrate 1400 covers the sensing region of working electrode 1230 1235.It is that it provides electrolytic contacts in the electrode layer 1200 with electrode, and generally (which is via electrolyte container 1410 The sky of the dielectric substrate formed in packaging area 1500 is not filled by part).In an other embodiments, electrode connects Tactile region 1250 is outside packaging area 1500, wherein produce electronics contacting to electrode.

Such as the 1500 encapsulated electrode layer 1200 of encapsulated layer, wicking layer 1300 and the dielectric substrate 1400 that show in Fig. 4 thus shape Into the integrated morphology with the porous substrate 1100 for not having material pass through in long-time.In addition the envelope as described in the figure 7 Dress layer 1500 includes capillary channel 1510, bucket volume 1520 and gas discharge hole hole 1530.In this embodiment, show and use Plastic foil punching operation forms capillary channel layer 1510 and bucket volume 1520 by polypropylene to produce profile.The cut gas Discharge hole.Encapsulated layer 1500 is heat-sealing to into porous matrix layers 1100.These feature permission electrolyte solutions are easily filled out Fill, but if wicking layer has contained electrolyte or electrolyte has been placed in above electrode before encapsulation step is taken, then not Need these features.

With reference to Fig. 8, the electrochemistry of the gaseous analytes produced in describing the illustrative sensors for Fig. 1-3 and Fig. 4-7 Reaction zone.Metallic catalyst (surface of working electrode) in working electrode, electrolyte (touching the surface of working electrode) and same Sample reaches and touches the surface of electrolyte and electrode and may be considered as the gas dissolved in the electrolyte in three-phase boundary region Three-phase boundary 840 at occur carbon monoxide electrochemical reaction.As shown in Fig. 8, CO (carbon monoxide converter) gas 810 pass through gas access Hole and entered by the hole of porous PTFE base material 820 and contacted at least partially with the catalyst particles of 830 moistening of electrolyte Grain 825.It should be appreciated that Fig. 8 is the schematic diagram in the electrochemical reaction area for gaseous analytes and not pro rata.Equally Ground, in some embodiments, catalyst granules 825 causes electric energy enough to pass by the catalyst granules 825 in physical contact Lead.

With reference now to Fig. 9 and Figure 10, show the exemplary version of the gas sensor 600 of printing.The gas sensing of printing Device 600 includes sensor layer 630, and the sensor layer 630 is connected to filter assemblies 610 simultaneously on the first side of sensor layer 630 And container assemblies 620 are connected on the second relative side.Sensor layer 630 is connected to encapsulated layer 680 comprising using PSA 650 Substrate layer 640.This forms integrated morphology and limits positioned at the electrolyte cavity between the substrate layer 640 and encapsulated layer 680 675.One or more electrodes 673 are connected to the core 670 (Figure 10) being placed in electrolyte cavity 675.Can be by substrate layer 640 are connected to filter assemblies 610 and encapsulated layer 680 can be connected to container assemblies 620.

In some embodiments, the gas sensor 600 of printing includes filter assemblies 610, and the filter assemblies 610 are included Charging port layer 613 and filtrate chamber ring 614.Plastics of the charging port layer 613 comprising molding or other suitable materials are (for example PET) and including one or more it is used for the filtration hole 612 that gas is entered in the filter assemblies 610.The filtrate chamber ring 614 include carbon or other suitable materials, the combination of such as 300LSE and PET.Filtrate chamber ring 614 is existed using PSA 650 The charging port layer 613 is connected on first side of the filtrate chamber ring 614 and PSA 650 is used in the filtrate chamber ring 614 The second relative side on be connected to substrate layer 640.PSA produces airtight sealing, and which is prevented in one or more filtrations except this Anywhere gas beyond hole 612 enters sensor layer 630 or filter assemblies 610.

When charging port layer 613 is connected to filtrate chamber ring 614 in the filtration mouth layer 613 times and the filtrate chamber ring Cavity is formed in 614.Filtering material 611 can be located in this cavity.Filtering material 611 can permit some object gas for example CO by and prevent some gases such as H₂S、HO₂、SO₂、O₂、NO₂, HCl passes through.Filtering material 611 can include Jingization Ground construction is learned to remove H₂S、HO₂、SO₂、O₂、NO₂, HCl, the hydro carbons that can be condensed, the C/KMnO of alcohols or the like₄Plug.The C/ KMnO₄Plug can include carbon cloth, activated carbon or be impregnated with KMnO₄Or other filtering materials of other reactive explosives.Can design Reactive explosive is preventing from disturbing the entrance of the entrance of gas simultaneously permission object gas or analyte.Or, filtering material 611 The KMnO on carbon and aluminium oxide can be included₄Mixture or other carbon mixs.In operation, gas can be entered in charging port Layer 613 top filtration hole 612 and reach filtering material 611.Can be through any gas of filtering material 611 (for example CO the sensor layer 630 of the gas sensor 600 of printing can) be entered.In some embodiments, the gas sensor of printing 600 do not include filter assemblies 610.In these embodiments, gas can be directly entered in sensor layer 630.

Referring still to Fig. 9, the gas sensor 600 of printing can include being connected to the sensing relative with filter assemblies 610 The container assemblies 620 of device layer 630.The container assemblies 620 are can act as in the electrolyte cavity 675 of sensor layer 630 The spilling chamber of the electrolyte 674 of setting.Environmental factorss such as relative humidity can cause electrolyte 674 and other liquid in electricity Expansion in solution matter cavity 675.Container assemblies 620 allow the electrolyte 674 of some expansions in the gas sensor 600 of printing The fluid expanded with other do not have destroy positioned at throughout printing gas sensor 600 airtight sealing in the case of stream enter In container assemblies 620.Expand to adapt to electrolyte 674, such as when the electrolyte 674 includes 4M H₂SO₄When, container assemblies 620 volume can be between the three times of the volume of dielectric substrate 675 and six times.This packing volume makes the gas sensor of printing 600 adapt to the energy when the gas sensor 600 printed used in high relative humidities (such as 95% relative humidity conditions) Enough fluid expansions for occurring.

Container assemblies 620 can include the container that hole 623 and container cavity ring 621 are overflowed with one or more containers Charging port layer 622.Plastics of the vessel filling mouth layer 622 comprising molding or other suitable materials, such as PET.The container cavity Plastics of the ring 621 comprising molding or other suitable materials, the combination of such as 300LSE and PET.By container cavity ring 621 at this Vessel filling mouth layer 622 is connected on first side of container cavity ring 621 and on the relative side of the container cavity ring 621 It is connected to sensor layer 630.One or more containers in vessel filling mouth layer 622 overflow hole 623 allows 674 Jing of electrolyte Container assemblies 620 enter the electrolyte cavity 675 (Figure 10) of sensor layer 630.Once electrolyte 674 enters electrolyte cavity 675, can airtightly seal or blocking container overflows hole 623, so as to protect liquid or gas to avoid except Jing gas accesses Sensor layer 630 is entered beyond region 643 (Figure 10).In some embodiments, the container assemblies 620 also comprising be connected to The container stopper 624 of the relative vessel filling mouth layer 622 of container cavity ring 621.The container stopper 624 airtightly sealing container can overflow Go out hole 623.In some embodiments, container stopper 624 is connected to after the filling electrolyte cavity 675 of electrolyte 674 Vessel filling mouth layer 622.In some embodiments, the container cavity ring 621 and the vessel filling mouth layer 622 be it is complete from And form complete spilling chamber or " bucket ".

With reference now to Figure 10, the sensor layer 630 of the gas sensor 600 of the printing of Fig. 9 is more fully described.Sensor Layer 630 includes the substrate layer 640 with the first local porous substrate 641 and the second local porous substrate 642, using in the face of should The PSA 650 arranged in the substantially whole surface of the first local porous substrate 641 of the second local porous substrate 642 incite somebody to action both Link together.The first local porous substrate 641 includes Merlon and the second local porous substrate 642 includes LSE And PET.In some embodiments, the first local porous substrate 641 and the second local porous substrate 642 can include which The plastics of his molding, such as PTFE.The first local porous substrate 641 enters sensor comprising permission gas such as object gas The gas inlet area 643 of layer 630.Gas inlet area 643 can be hole.Gas inlet area 643 can also be and pass through Porous in the first local porous substrate 641 of the formation of first local porous substrate 641 is coated optionally with polyimides Region.The region of the first local porous substrate 641 covered with polyimides hinders gas to enter and no polyimides The region of the first local porous substrate 641 forms gas inlet area 643 so as to allow to include one or more object gas Gas enters sensor layer 630.The second local porous substrate 642 can be arranged in groove 644 comprising being configured such that The groove 644 of PTFE disks 645.Groove 644 be located at it is substantially coaxial with gas inlet area 643 and can have with diameter greater than this The diameter of gas inlet area 643 causes when PTFE disks 645 are placed in groove 644 it to be connected to be suspended from the groove 644 The first local of part porous substrate 641 and substantially coaxial with gas inlet area 643.The PTFE disks 645 can be wrapped Such as MuPore of PTFE film containing Local Porous.The gas Jing PTFE disks of sensor layer 630 are entered by gas inlet area 643 645 spread and reach the electrode 673 that is placed in electrolyte cavity 675.It should be appreciated that substrate layer 640 alternatively can be included Single Local Porous base material, which includes one or more gas inlet areas and also including for accommodating the groove of PTFE disks.

Substrate layer 640 can also include the runner 646 of the printing being directly printed on the second local porous substrate 642.Should The runner 646 of printing faces electrolyte cavity 675 and comprising the non-porous hydrophobic material for not absorbing any electrolyte 674. By 646 punching press of runner of printing, vapour deposition or can be similar to the second local porous substrate 642.Make the runner 646 of printing Patterning, it is allowed to which it is connected with the various electrodes 673 in electrolyte cavity 675.In some embodiments, the runner of printing 646 conductive traces comprising one or more with conductive ink.

Referring still to Figure 10, encapsulated layer 680 is included and is entered with one or more electrolyte for being connected to package cavity ring 683 The electrolyte charging port layer 681 in oral pore hole 682.The modeling of the electrolyte charging port layer 681 and the package cavity ring 683 comprising molding Material such as PET, or the combination of LSE and PET.Package cavity ring 683 is connected to into relative with electrolyte charging port layer 681 also Two Local Porous base materials 642.In electrolyte charging port layer 681, package cavity ring 683 and the second Local Porous of substrate layer 640 PSA 650 is set between base material 642, its airtightly hermetically sealed layer 680 and electrolyte for being formed in package cavity ring 683 Cavity 675.The electrolyte cavity 675 can accommodate electrolyte 674 and be connected to the core 670 of one or more electrodes 673.One In a little embodiments, electrolyte charging port layer 681 and package cavity ring 683 form single complete " bucket " structure, and the structure connects It is connected to the second local porous substrate 642 and accommodates electrolyte cavity 675.Electrolyte inlets in electrolyte charging port layer 681 Hole 682 allows electrolyte 674 to enter electrolyte cavity 675.

Sensor layer 630 described in Figure 10 is also comprising one or more electrodes 673 for being connected to core 670.Core 670 can Comprising cellular glass fiber or glass fiber filter paper.In this embodiment, by one or more 673 silk screen printings of electrode, spray Ink print, punching press or template spary are to core 670.Can in the gas sensor 600 for be assembled to core 670 printing before will Electrode 673 is printed or is cured on core 670.For example, can use 673 embedded core 670 of electrode and produce with trizonal core- Electrode assemblie.First area only includes core 670, and second area includes the electrode 673 being embedded in the core 670, and the 3rd region It is only included in the electrode 673 extended on the core 670.Second area is classified and is caused when by (only including with the first area Contain and gradually increase to the second area during boundary survey with the 3rd region (only comprising electrode 673) in core border 670) Electrode 673.By this transition of core 670 to electrode 673 promote the close contact of 674 Jing cores 670 of electrolyte to electrode 673 with Transition, so as to encourage moistening.Additionally, core-the electrode assemblie produces strong structural combination between electrode 673 and core 670.

The fibrous glass or fibrous glass filter paper of core 670 can be resistant to the material of the material or encapsulated layer 680 than substrate layer 640 Higher temperature.For example, core 670 can be resistant to about 300 DEG C of solidification temperature.This permission is being assembled to the gas sensor of printing One or more electrodes 673 are cured on core 670 before in 600.Core 670 or compressible.In some embodiments, Initial height of the height of electrolyte cavity 675 less than core 670.When core 670 is assembled in electrolyte cavity 675, in electricity Core 670 is compressed so as to install in solution matter cavity 675.

One or more electrodes 673 can include and be mixed with metallic catalyst and additive to form the pitch-dark compound electrics of PTFE The PTFE of pole is black.Especially, one or more electrodes 673 can include the Pt of 1.44-1.45g, the graphitic carbon of 0.16 ± 0.1g With the Teflon suspensions (PTFE of 0.48g) of 0.80-0.81g.The Teflon suspensions can be less than the TFE of 1 μ m diameter The mixture of granule, water, surfactant and 3mL ethyl cellulose solutions.In some embodiments, with by dry PTFE Ink prepared by granule rather than PTFE aqueous solutions is printing electrode 673.In other embodiments, with by polypropylene powder or Ink prepared by polyethylene powders is explained in further detail below printing electrode 673.

Referring still to Figure 10, the core 670 for there are one or more electrodes 673 is placed in electrolyte cavity 675.Once will Core 670 is assembled in electrolyte cavity 675, and the electrode 673 being placed on core 670 can be coordinated with the runner 646 of printing.As general Such as H of electrolyte 674₂SO₄When being introduced in electrolyte cavity 675, the electrolyte 674 contacts core 670.Electrolyte 674 can penetrate into In core 670 and contact electrode 673.Once the electrolyte 674 and electrode 673 are contacted and object gas such as CO Jing gas accesses Region 643 enters the gas sensor 600 of printing, and electrochemical reaction is just produced in electrolyte cavity 675.The electrode 673, Electrochemical reaction between the electrolyte 674 and object gas produces electric current and in the runner 646 of printing at one or many The signal of telecommunication is sent to the runner 646 with printing at individual electrical pickoff 661 one or more circuits being connected.This signal of telecommunication is to one Individual or multiple circuit communications：Object gas are detected in the gas sensor 600 of printing.

Referring still to Figure 10, the runner 646 of printing faces core 670 and contacts at least one electrode 673 and along this The length of the runner 646 of printing extends.The embodiment of replacement can include the runner 646 of two or more printings.Even At one or more electrical pickofves 661 for the outer portion for being connected to the runner 646 of printing, the runner 646 of the printing terminates.Electrical contact Point 661 promotes the electrical connection between runner 646 and one or more circuits, wire in printing or the like.This allow by The electric current that electrochemical reaction between electrode 673, electrolyte 674 and object gas is produced along the printing runner 646 by electricity Pole 673 is moved to one or more circuits.One or more circuits are arranged on a printed circuit can.This one or more Circuit can use the electric current produced by electrode 673, electrolyte 674 and object gas to come trigger or alarm function.Replacing In the embodiment in generation, substrate layer 640 can not include the runner 646 of printing.In this embodiment, by the runner of printing 646 are connected to the Local Porous base material in the face of core 670.In some embodiments, the runner 646 of printing includes one or more Conductive trace with conductive ink.

With reference now to Figure 11 A, with the embodiment that exploded view describes Fig. 9 and Figure 10.With reference now to Figure 11 B, with what is printed Form describes filter assemblies 610, container assemblies 620 and the sensor layer 630 of Fig. 9 and Figure 10.Although Figure 11 A and Figure 11 B is described Optional filter assemblies 610 and optional container assemblies 620, it should be appreciated that contemplate no filter assemblies 610 or container The embodiment of the gas sensor 600 of the printing of component 620.

With reference now to Figure 12, description is included in can at a temperature of the fusing point and deformation point of the material less than sensor layer 730 The sensor layer 730 of the embodiment of the gas sensor 700 of the printing of one or more electrodes 773 of solidification.The sensor Layer 730 includes the solid substrate 741 for being connected to encapsulating housing 781 so as to be formed between solid substrate 741 and encapsulating housing 781 Electrolyte cavity 775.The solid substrate 741 can be the gas sensor to allow gas into printing of Local Porous 700.By solid substrate 741 optionally being coated with polyimides can form gas inlet area 743.By coated polyimide The region barrier gas of the solid substrate 741 of lid enter and do not have the region of solid substrate 741 of polyimides to form gas Entrance area 743 enters sensor layer 730 so as to allow the gas for including one or more object gas.The gas inlet area 743 can also be one or more holes.The solid substrate 741 or hydrophobic and oleophobic preventing from entering electrolyte absorption With the obstruction gas inlet area 743 in solid substrate 741.The encapsulating housing 781 includes one or more encapsulation holes 782. The solid substrate 741 and the encapsulating housing 781 include cold plastics such as polycarbonate substrate and PET base material.Merlon base Material and PET base material are chemically inert and with the fusing point less than or equal to 260 DEG C.Additionally, one or more are printed Runner 760 is connected to solid substrate 741 and constructs the runner 760 of one or more printings will produce in electrolyte cavity 775 Raw electric current is delivered to one or more contact points 761.One or more contact points 761 can be with one or more circuit examples As printed circuit board (PCB) makes electrical contact with.

In the embodiment for describing in fig. 12, one or more electrodes 773 are directly printed on solid substrate 741. The electrode 773 is made up of ink composition, the ink composition less than solid substrate 741 and both fusing points of encapsulating housing 781 or Solidify at a temperature of deformation point.The whole sensor layer 730 of this permission melts the solid substrate 741 or the encapsulating housing no The curing process of electrode 773 is experienced in the case of 781.One exemplary low-temperature electrodes ink composition is comprising polypropylene, catalysis The polypropylene miser of agent, solvent and additive (such as the platinum on the catalyst of platinum, palladium or alloy or load such as carbon).Another Exemplary electrode ink composition includes polyethylene, catalyst, solvent and additive (such as catalysis of platinum, palladium or alloy or load Platinum in agent such as carbon).These electrode ink compositions solidify at a temperature of less than or equal to 250 DEG C and can form local to be dredged The porous gas diffusive electrode of water.Additionally, the electrode 773 printed by these electrode ink compositions and electrolyte 774 and target gas Body forms three-phase boundary.When electrolyte 774 contacts electrode 773,70 ° or bigger contact angle are formed, so as to local moistening should Electrode 773.For example, comprising H₂SO₄Electrolyte 774 can have 75 ° or bigger contact angle.Printing described in Figure 12 Gas sensor 700 is further included in the container assemblies and filtration group that the opposite side of sensor layer is connected to the sensor layer Part.The filter assemblies and the container assemblies can be and the embodiment identical or essentially similar described in Fig. 9.

With reference now to Figure 13, the sensor layer 930 of the gas sensor 900 of display example printing,.Sensor layer 930 is wrapped Containing being partially coated with polyimides to form base material 941 on the high temperature of one or more porous gas entrance areas 943.It is coated with On the high temperature of polyimides, the region barrier gas of base material 941 are entered and do not have the area of base material 941 on the high temperature of polyimides Domain forms gas inlet area 943 to allow the gas for including one or more object gas to enter sensor layer 930.At some In embodiment, gas inlet area 943 can include one or more holes.Using one or more sealing member spacers Base material on high temperature 941 is connected to base material 942 under high temperature by 990, so as to be formed in base material 941 and base material under the high temperature on the high temperature Electrolyte cavity 975 between 942.The sealing member spacer 990 is welded using thermoplastic welding strip or other exemplary plastics Method can be used in the solid material that base material on high temperature 941 is soldered to base material 942 under high temperature.In this welding procedure, The material and the material for optionally melting the sealing member spacer 990 can penetrate on high temperature base under base material 941 and high temperature In the hole of material 942；Tighten together base material under base material on high temperature 941 and high temperature 942 glued, welding or otherwise.This Form airtight sealing and produce the electrolyte cavity 975 on the high temperature under base material 941 and high temperature between base material 942.One In a little embodiments, on the high temperature, under base material 941, the high temperature, base material 942 or both can be Local Porous.Covered using UV Technique makes each patterning of base material 941,942 form this local hole by material with photoresist.

On high temperature, under base material 941 and high temperature, base material 942 can be comprising PTFE, polyimides or any other high temperature, chemistry Inert material and sealing member spacer 990 can include FEP or other chemical inertnesses, flowable bond material, the material The eroding chemical used in electrolyte, electrode and analyte can be sustained and 260 DEG C or higher can be sustained Temperature.On high temperature, under base material 971, high temperature, the material of base material 972 and sealing member spacer 990 can sustain at least 260 DEG C Solidification temperature.For example, polyimides can sustain at most about 400 DEG C of temperature and PTFE can be sustained at most about 330 DEG C of temperature.These high-temperature materials allow sensor layer 930 to be assembled on circuit board during board production and Sensor layer 930 is placed in the solder reflow furnace at 260 DEG C and continues the various time periods, such as nine seconds.

One or more electrodes 973 are connected on the high temperature base material 941 using ink-jet or screen printing technique and are placed In electrolyte cavity 975.One or more electrodes 973 may be embodied in temperature from about 260 DEG C to about 330 DEG C (for example 300 DEG C) electrode that combines of the TFE of curable.The electrode can include PTFE ink, metallic catalyst, solvent and additive.Can Interacted to produce electrochemical reaction and produce electric current with electrolyte 974 and object gas with constructing some electrodes 973. Other electrodes work as bunny testers or conductivity tester.The electrode as conductivity tester work can be constructed 973 can test and monitor electrolyte 974 continually or intermittently checking the battery whether to run the appropriate and electrode 973 Concentration.In some embodiments, the different object gas of 973 each Autonomous test of multiple electrode can be constructed.For example, first Electrode 973 can detect CO and second electrode (not shown) being capable of detected gas such as H₂S、O₃、SO₄Or NO₂.Electrolyte is empty Chamber 975 can be partially filled with contacting each electrode 973 and the core with each electrode 973 of 974 moistening of electrolyte.Additionally, Electrolyte 974 includes H₂SO₄Embodiment in, depending on printing gas sensor 900 around environment relative humidity, The volume of electrolyte 974 being capable of expansion or shrinkage.In high relative humidity conditions, the volume of the electrolyte 974 of fixed amount can be swollen Swollen three times are accumulated to hexaploid.As being more fully described above, can construct and be connected to the container assemblies of sensor layer 930 to hold Receive the electrolyte of spilling.

Referring still to Figure 13, the electrolyte cavity 975 for airtightly sealing accommodates one or more electrodes 973 and electrolyte 974, produce the position for the electrochemical reaction between electrode 973, electrolyte 974 and object gas.Base material on high temperature 941st, under high temperature, the material of base material 942 and sealing member sept 990 such as PTFE can be electrochemicaUy inert；Without generation Allow in the case of chemical reaction under base material 941, high temperature on high temperature between the material of base material 942 and electrolyte 974 any Electrolyte 974 enters electrolyte cavity 975.Exemplary electrolyte 974 includes caustic acid, alkali and salt, such as H₂SO₄, which can Sustain at most 340 DEG C of solidification temperature.Other exemplary electrolytes 974 include solvent and RTIL, can for example sustain to The ionic liquid of many 360 DEG C of solidification temperature.

Referring still to Figure 13, the runner 960 of printing is connected to into the base material 941 on the high temperature of electrolyte cavity 975.Structure The runner 960 for making the printing delivers the electric current produced in electrolyte cavity 975 to one or more contact points 961.Should One or more contact points 961 can be made electrical contact with one or more circuits (such as printed circuit board (PCB)).The runner 960 of the printing Can make up and functionally with regard to Figure 10 and Figure 12, described above those are identical.The gas sensor 900 of the printing is also The opposite side that may be embodied in the sensor layer 930 is connected to the container assemblies and filter assemblies of sensor layer.The filter assemblies With the container assemblies can be and the embodiment identical or essentially similar described in Fig. 9.

The diameter of the arbitrary gas access hole of embodiment described above can be changed to change mesh in sensor layer The range of sensitivity of mark gas detecting.In each embodiment, the amount into the gas of sensor should be anti-with sensor Answering property is matched.When gas access hole diameter increases, should there are more catalyst to optimize the gas of printing in electrode The signal to noise ratio of sensor.For example, the gas access hole with 1mm diameters can match with the WE catalyst of 5-10mg and 0.25mm gas accesses hole can be matched with 2.5mg catalyst.Detection range and output based on the gas sensor of printing It is required to select specific sensitivity and signal to noise ratio.For example, high object gas detection range is in about 0ppm and about 1000ppm Between and low target gas detecting scope is in about 0ppm and about between 10ppm.There is the printing of low target gas detecting scope Gas sensor by the gas sensing with the printing than there is high object gas detection range less catalyst and less Gas access hole.Proportional level of sensitivity in the gas sensor of object matching generation printing.For example, there is low target gas The gas sensor of the printing of body detection range can partly detect low-level object gas, because it can make background make an uproar Sound is minimized.Equally, the gas sensor for having the printing of high object gas detection range can detect high-caliber object gas While resistance to high-caliber background noise.

In embodiment described here, electrolyte acid concentration can be selected to match the gas sensing by printing is used Relative humidity in the environment of device.For example, should if the relative humidity of environment is greater than 95% continuous (such as colliery) Using about 1M acid electrolytes.If the relative humidity of environment, should be using about less than 10% (such as dry gas) 10M acid electrolytes.In some embodiments, single sensor design can be relatively wet what is changed from 5-95% relative humiditys Work in degree environment.In these embodiments, the gas sensor of printing can also include that the gas for being connected to the printing is passed The container assemblies of the sensor layer of sensor.The environment of the relative humidity with change can cause electrolyte expansion and contraction.It is logical Cross including the container assemblies, in the case where the airtight sealing of sensor layer is not destroyed, electrolyte can expand and shrink Enter the container assemblies.In some embodiments, container assemblies should have the several times volume of electrolyte cavity.For example, work as electricity Solution matter is H₂SO₄When, the volume of the container assemblies can be the three times of the volume of the electrolyte cavity to six times.

In some embodiments, porous electrode includes the polymers compositionss for substituting.In some embodiments, electrode package PTFE granules are dried containing standard PTFE aqueous dispersion granule is replaced.In some embodiments, contained with replacement standard PTFE The PP GRANULES of aqueous dispersion granule prepares electrode.In some embodiments, polyethylene particle replaces standard PTFE granule. The advantage with polymer replacement PTFE for noting above is that electrode will solidify at a lower temperature.This allows electrode direct Print to plastic basis material and part.The electrode can be cured on plastic basis material and part in packaging technology.Need not It is special to process or pick up and placement operation.This can reduce and simplify procedure of processing.

In any embodiment described above, the manufacturing process of the gas sensor of printing can be it is extendible, Large Copacity piece (such as gas sensor with 60 printings for example in the gas sensor comprising 10-100 printing per piece Piece).In some embodiments, extendible manufacturing process can be given birth in one or more can be the piece of various sizes Produce the gas sensor of the printing of various embodiments.For example, in 2 × 5 of the sensor comprising 10 printings, including In 5 × 5 of gas sensors of 25 printings, in 10 × 10 of the gas sensors comprising 100 printings or can expand Sensor (the printed as of printing state can be manufactured in any other size and dimension of the piece of the manufacture of exhibition sensor).It should be appreciated that the technique of the gas sensor of manufacture printing can progressively be extended to any required size, example Gas sensor, the gas sensor of 1000 printings or more pieces such as with 500 printings.

In some embodiments, electrode is prepared with ethyl cellulose solution.In this embodiment, by the 10cP's of 5g Ethyl cellulose is dissolved in 75mL isophorone 25mL DAA solution.By in the container for have lid at 50 DEG C to 75 DEG C Under stirred dissolve the solution yesterday.In some embodiments, reduce the capryl alcohol of toxicity and abnormal smells from the patient to replace 75mL with 75mL Isophorone.The isophorone in ethyl cellulose solution can also be replaced using other solvents such as nonyl alcohol or decanol.Should Solvent must be with least for the least polar required for two acetone of dissolving.In preferred embodiments, the solvent is with slow Slow speed evaporation.In some embodiments, ethyl cellulose can be added to adjust the viscosity for printing.Preferred In embodiment, the dispersion stable, with low evaporation rate and good viscosity.When the electrode is solidified (typically at 60 DEG C And between 250 DEG C, in not damaging at a temperature of plastic basis material) solvent has to leave behind combination electrode.

In some embodiments, the catalyst ink suspension of the electrode package weight containing 23-25 %PTFE.More specifically, The PTFE suspensions of Pt, the graphitic carbon of 0.16 ± 0.01g and .80-.81g of the catalyst ink suspension comprising 1.44-1.45g Mixture, the PTFE suspensions include the PTFE granules less than 1 μm of 0.48g, water, surfactant and 3mL ethyl celluloses Plain solution or octanol solution.

In some embodiments, by dry PTFE granules rather than standard PTFE aqueous solution prepare ink.By dry PTFE powder prepares dry PTFE granules and the PTFE granules of drying directly suspend in a solvent.Contain without they are placed in In water slurry such as standard PTFE dispersion.Produced by the electrode of dry PTFE particle preparations and prepared using PTFE aqueous solutions Electrode response 20-45%.Electrode and include PTFE water that Figure 14 explanations include the 23% and 30% PTFE granules being dried Response signal of the electrode of solution in terms of μ Amps.In Figure 14 from left to right signal peak measure respectively 50ppm object gas, The addition of 100ppm object gas and 400ppm object gas.

In some embodiments, electrode is prepared using low temperature adhesive such as polypropylene and polyethylene powders.These powder End is hydrophobic adhesive.Density of the density of the density and polyethylene (PE) of polypropylene (PPRO) less than PTFE.(PTFE= 2.0-2.2g/cc；PPRO=0.93g/cc；PE=0.97g/cc).Due to relatively low density, the optimization weight for PPRO and PE Amount percentage ratio is less than PTFE (15-17wgt%PPRO, PE are to 23-25wgt%PTFE).

In some embodiments, PPRO catalyst inks suspension comprising 1.44-1.45g Pt (74-78wgt%), The graphitic carbon (8-9wgt%) of 0.16 ± 0.01g, the PPRO powder (14-17wgt%) of 0.25-0.30g and the ethyl cellulose of 3mL The mixture of plain solution.Response by the electrode of 5-7 μm of PPRO particle preparations is the sound of the electrode prepared by PTFE aqueous solutions The about 10-20% for answering.In some embodiments, Pt of the PE catalyst inks suspension comprising 1.44-1.45g (74-78 weights Amount %), the graphitic carbon (8-9 weight %) of 0.16 ± 0.01g, the PE powder (14-17 weight %) of 0.25-0.30g and the second of 3mL The mixture of base cellulose solution.Response by the electrode of 2-4 μm of PE particle preparations is the electrode prepared by PTFE aqueous solutions Response about 25-30%.

In some embodiments, electrode sensitivity can be optimized by reducing catalyst particle diameter.Figure 17 explanations are poly- Impact of the polymer beads diameter to the sensitivity of the electrode comprising 17-23wgt% polymer and 77-83wgt%Pt, with regard to nominal Signal (μ A/ppm) of polymer particle diameters (μm) measurement per ppm.CO sensitivity do not rely on specific polymer (if it is full Foot is for the requirement of appropriate three-phase boundary), but it is depending on the size of granule.For example, less granule increases CO sensitivity. In some embodiments, sensor can be optimized to sensor performance by reducing gas access hole diameter.In a reality It is in example, such as illustrated in fig. 18, by gas access diameter is reduced to 1.0mm by 1.5mm, sensor is improved to sensor Change.In some embodiments, by 3mm in terms of gas open area²To 1mm²Reduction reduced with the coefficient of about 2.5-3.0 The amount of signal (by 50nA/ppm to 20nA/ppm) and also the background noise for reducing entering sensor.Signal and noise two Person can be with catalyst area linear reduction.When the girth of gas open area is increased with area ratio, exist in terms of signal to noise ratio Improve.By gas access hole diameter is matched the sensitive of the gas sensor that can optimize printing with the size of electrode layer Degree.For example, with 3mm diameters and 2.5mg/cm²The electrode layer of 5-7 mil thicks of catalyst can optimize to have and have The gas sensor of the printing of the gas access hole of 0.5mm diameters.

If although discussing equipment for drying and its component in detail above, it should be appreciated that the part that discussed, feature, structure Make the context that uniqueness provided above is not restricted to integrated and using the device for being discussed method.Especially, can be by Part, feature, construction and using method described in the context of one of the device is integrated with or goes out arbitrary other devices. Additionally, be not limited to be provided below further describes, the suitable part of extra and replacement, feature, construction and preparation and make With the method for device, and can be combining and exchange the various modes of teachings herein in view of teachings herein is common to this area Technical staff will be apparent.

Various versions are had been shown and described in the disclosure, and those skilled in the art are not leaving the model of the present invention The further modification of method and system described herein can be completed in the case of enclosing by appropriate modification.It has been mentioned that some Such potential modification, and others are will be apparent to those skilled in the art.For example, examples discussed above, scheme, Geometric figure, material, size, ratio, step and its it is similar be illustrative and not required.Therefore, it should according under Row claim considers the scope of the present invention and it should be appreciated that the scope of the present invention is not limited to show in the specification and illustrated in the drawings With the details structurally and operationally of description.

Experiment

In the following experiments, the polymers compositionss for substituting used in the formation of Porous gas electrode.Using comprising difference The catalysis ink suspension of polymers compositionss is producing electrode.Test and measure these electrodes.Especially, respectively with drying PTFE granules, PP GRANULES and polyethylene particle replace the standard PTFE aqueous dispersion being catalyzed in black suspension to carry out reality Test.Also carry out with the target of optimization CO sensitivity, the signal to noise ratio for optimizing sensor to sensor performance and improving sensor Experiment.

Pt of the standard PTFE catalyst ink suspension comprising 1.44-1.45g, the graphitic carbon of 0.16 ± 0.01g and .80- The mixture of PTFE suspensions .81g, PTFE granule less than 1 μm of the PTFE suspensions comprising 0.48g, water, surface activity Agent and 3mL ethyl cellulose solutions or octanol solution.The ethyl cellulose solution is the ethyl cellulose of the 10cP of 5g and include 75mL isophorones and 25mL DAAs solution mixing combination, the solution on hot plate have the container of lid in be in Stirred solvent soln yesterday at 50-70 DEG C.In order to form standard PTFE catalyst ink suspension, by Pt, graphitic carbon, PTFE, Ethyl cellulose, water and surfactant using sonication mix and using silk screen printing or template spary technique be dispersed to core or Then solidify on base material.When standard PTFE catalyst ink suspension solidifies, evaporation is left combination electrode by solvent.It should be appreciated that Catalyst ink suspension is dispersed to by the technique to catalyst ink suspension sonication, using silk screen printing or template spary On core or base material, and then curing catalysts ink suspension, the embodiment of catalyst ink suspension described herein any one Electrode can be formed.

Isophorone can also be replaced to form the ethyl cellulose solution using capryl alcohol, nonyl alcohol or decanol.Capryl alcohol is than different Phorone has less toxicity and less abnormal smells from the patient.The solvent for using can have a small amount of polarity so as to dissolving two acetone and should not This evaporates too quickly.Solvent can also dissolve some additive ethyl celluloses to adjust the viscosity for printing.This can lead Cause stable dispersion, low evaporation rate and good viscosity.

Experiment 1

In experiment 1, by dry PTFE powder rather than standard PTFE dispersion (TFE-30^TMPTFE) prepare catalyst Black suspension is determining the difference responded between electrode by made by dry and aqueous PTFE catalyst inks.By dry PTFE Pt (67-71wgt%), the graphitic carbon (7- of 0.16 ± 0.01g of the catalyst ink suspension that powder is formed comprising 1.44-1.45g 8wgt%), the mixture that the PTFE powder (22-25wgt%) of 0.48-0.49g is combined with the ethyl cellulose solution of 3mL.It is dry The particle diameter of dry PTFE powder is about 1-5 μm.This granule than the standard PTFE dispersion with no more than 1 μm of granule Diameter is big.Electrode of Figure 14 explanations comprising the 23% and 30% PTFE granules being dried and the electrode comprising PTFE aqueous solutions are with μ The response signal of Amps meters.In Figure 14 from left to right signal peak measure respectively 50ppm object gas, 100ppm object gas and The addition of 400ppm object gas.As being illustrated in Figure 14, by the catalyst ink suspension shape comprising dry PTFE powder Into electrode produce by standard PTFE dispersion prepare electrode response 20-45%.Dry PTFE's is relatively low sensitive Degree is apparently relevant with particle diameter.This size is described in detail in following experiment 4 with the relation of sensitivity.

Experiment 2

Experiment 2 in, by polypropylene (PPRO) powder (hydrophobicity adhesive) rather than PTFE prepare catalyst ink suspension Liquid.PPRO is binded at the temperature lower than PTFE.The PPRO powder particles for using are about 5-7 μm.The optimization weight of PPRO powder Percentage ratio is less than PTFE because with PPRO lower than PTFE density.The density of PTFE is the density of 2.0-2.2g/cc and PPRO For 0.93g/cc.The optimization percentage by weight of PTFE is 23-25wgt% and the optimization percentage by weight of PPRO is for about 15- 17wgt%.Pt (75-79wgt%) of the catalyst ink suspension formed by PPRO powder comprising 1.44-1.45g, 0.16 ± The graphitic carbon (8-9wgt%) of 0.01g, that the PPRO powder (14-17wgt%) of 0.25-0.30g is combined with 3mL ethyl celluloses is molten The mixture of liquid.

Response signal of the electrode that Figure 15 explanations are formed by 5-7 μm of PPRO powder particles in terms of μ Amps.From a left side in Figure 14 Measured to right signal peak respectively CO, 5000ppm of CO, 2500ppm of CO, 1000ppm of CO, 500ppm of 250ppm CO and The addition of the CO of 250ppm.About 10-20% of the PPRO powder electrodes response for standard PTFE electrode response signal.PPRO electrodes ratio PTFE electrode responses and recover slowly.

Experiment 3

In experiment 3, by polyethylene (PE) powder (hydrophobicity adhesive) rather than PTFE prepares catalyst ink suspension. PE is binded at the temperature lower than PTFE.The PE powder particles for using are about 2-4 μm.The optimization percentage by weight of PE powder is less than The optimization percentage by weight of PTFE is because PE is with the density lower than PTFE.The density of PTFE is the close of 2.0-2.2g/cc and PE Spend for 0.97g/cc.The optimization percentage by weight of PTFE is 23-25wgt% and the optimization percentage by weight of PE is for about 15- 17wgt%.Pt (75-79wgt%) of the catalyst ink suspension formed by PE powder comprising 1.44-1.45g, 0.16 ± The graphitic carbon (8-9wgt%) of 0.01g, the PE powder (14-17wgt%) of 0.25-0.30g are combined with 3mL ethyl cellulose solutions Mixture.

Response signal of the electrode that Figure 16 explanations are formed by 2-4 μm of PE powder particles in terms of μ Amps.PE powder electrodes ring Should be the about 25-30% of standard PTFE electrode response.In here experiment, PE electrodes are than PTFE electrode response and recover slowly.This A little results show to optimize needs of the composition to improve three-phase boundary condition.

Experiment 4

Relation between the particle diameter of the polymer used in the CO sensitivity of Figure 17 explanation electrodes and electrode.By drop Low particle diameter is possible come the CO sensitivity for increasing electrode.Data in Figure 17 illustrate polymer particle diameters to including The impact of the sensitivity of the electrode of 17-23wgt% polymer and 77-83wgt%Pt.The CO sensitivity of electrode is with polymer beads Diameter change.According to this experiment, sensitivity does not rely on specific polymer.If meeting wanting for appropriate three-phase boundary Ask, then polymer particle diameters become for adjusting the significant variable of CO sensitivity.

Experiment 5

Figure 18 illustrates gas port size and sensor to the relation between sensor consistency.In experiment 5, sensor Gas port size is reduced to 1.0mm diameters by 1.5mm diameters.This reduce by sensor to sensor consistency be improved to about ± 5%.

Experiment 6

In experiment 6, by the gas open area of sensor by 3mm²It is reduced to 1mm², coefficient 9.This by sensor signal by 50nA/ppm is reduced to 20nA/ppm, coefficient about 2.5-3.0.Sensor base is shown by the conventional work of Dr.Stetter and colleague Line current is linearly reduced with catalyst area and signal to noise ratio is improved when girth is increased with area ratio.For example, see Buttner, W.J., the United States Patent (USP) 5,512,882 that Maclay, G.J., and on April 30th, Stetter, J.R., 1996 announces “Chemical Sensing Apparatus and Methods,”；Buttner,W.J.,Maclay,G.J.,and Stetter,J.R.,“Microfabricated Amperometric Gas Sensors with an Integrated Design,”Sensors and Materials,2,99-106,(1990)；Buttner,W.J.,Maclay,G.J.,and Stetter,J.R.,“Microfabricated Amperometric Gas Sensors”IEEE Trans.On Electron Devices 35(6),793(1988)；And Buttner, W.J., Maclay, G.J., and Stetter, J.R., " An Integrated Amperometric Microsensor,”Sensors and Actuators,B1,303-307,(1990)。

It should be appreciated that the less sensor generally realized by design described herein and manufacture method causes sensor expand Open up to prior art be not reaching to size, wide temperature range it is operable, and by expansible approach to caused by producing being Low cost.The gas sensor of printing described herein can also work simultaneously in the environment of the relative humidity with wide scope Signal to noise ratio with the extendible optimization that can be used for detecting low or high-caliber object gas.

The described above of embodiment of the present invention and embodiment is presented for the purpose of illustration and description.It is not intended to Limit or invention is limited to into described form.It is possible according to many modifications of teaching above.Discuss one A little those modifications and it will be appreciated by those skilled in the art that other modifications.Although many embodiments here disclose detection CO Printing gas sensor, sensor described herein and manufacture method can be constructed to measure other object gas for example H₂S、NO₂、SO₂And it is similar.The embodiment is selected and is described to be best described by the principle of the present invention and to be suitable for contemplated Particular utility various embodiments.Certainly, the scope of the present invention is not limited to embodiments set forth here or embodiment, but It is can be used in any amount of application and equivalent device by those skilled in the art.More properly be intended to hereby by The scope of the present invention is limited in the claim appended by this.

Claims

1. the gas sensor for printing, which includes：

The first local porous substrate comprising one or more gas inlet areas；

The runner of one or more printings of the first local porous substrate is connected to,

Wherein

The runner of one or more printings is non-porous and conductive；

Encapsulated layer, the encapsulated layer are connected to the first local porous substrate and limit the electrolyte sky in the encapsulated layer Chamber；

The core being placed in the electrolyte cavity；

The electrode of one or more printings, which is printed on the core and runner telecommunication of one or more printings with this The runner of one or more printings is enabled to transmit the e-mail produced by the electrochemical reaction of one or more electrodes Number；With

It is contained in the electrolyte cavity and the electrolyte that the electrode of communication communicates can be electrolysed in-between the electrodes.

2. the gas sensor of the printing of claim 1, wherein the first local porous substrate include porous PTFE, in the porous Partly block one or more holes by the non-porous materials for being attached to the base material in PTFE.

3. the gas sensor of the printing of claim 2, wherein being made using mask and flat board printed reagent by the non-porous material One or more sectional hole patterns of material local obstruction.

4. the gas sensor of the printing of claim 1, also comprising be placed on the first local porous substrate and the encapsulated layer it Between the second local porous substrate, wherein the second local porous substrate also includes and groove and places porous PTFE in the groove Disk.

5. the gas sensor of the printing of claim 1, also comprising be placed on the first local porous substrate and the encapsulated layer it Between the second local porous substrate, wherein the second local porous substrate also includes and groove and places porous polypropylene in the groove Or polyethylene pan, wherein the electrolyte is with the electrolyte contact angle more than 70 degree.

6. the gas sensor of the printing of claim 5, wherein the second local porous substrate include poly terephthalic acid second two Alcohol ester.

7. the gas sensor of the printing of claim 1, the wherein encapsulated layer comprising electrolyte charging port layer and be placed on this Between one Local Porous base material and the electrolyte charging port layer and the package cavity ring of the two is connected to, thus in the package cavity The electrolyte cavity is formed in ring.

8. the gas sensor of the printing of claim 1, the wherein core include the electrolyte matrix selected from following one or more： Compressible fibrous glass, the hydrophilic polypropylene of porous or polyethylene, silica gel or aluminium oxide.

9. the gas sensor of the printing of claim 1, wherein before the core is placed in the electrolyte cavity by this one Individual or multiple electrodes are printed on the core.

10. the gas sensor of the printing of claim 9, wherein being sprayed using silk screen printing, intaglio printing, ink jet printing or template Brush is by one or more electrode prints on the core.

The gas sensor of the printing of 11. claim 1, wherein one or more electrodes are partly nested in the core.

The gas sensor of the printing of 12. claim 1, wherein one or more gas inlet areas include hole.

The gas sensor of the printing of 13. claim 1, wherein the first local porous substrate are partly coated with polyimides So that one or more uncoated areas of the first local porous substrate comprising one of the first local porous substrate or Multiple gas inlet areas.

The gas sensor of the printing of 14. claim 1, wherein arranging between the first local porous substrate and the encapsulated layer Pressure-sensitive adhesive agent.

The gas sensor of the printing of 15. claim 1, wherein arranging between the first local porous substrate and the encapsulated layer Hot adhesive.

The gas sensor of the printing of 16. claim 1, wherein using combination of ultrasound by the first local porous substrate and the envelope Dress layer welds together.

The gas sensor of the printing of 17. claim 1, the wherein runner of one or more printings are contacted at one or more Terminate so as to provide the telecommunication between one or more electrodes and one or more circuits at point.

The gas sensor of the printing of 18. claim 1, the runner of wherein one or more printings are formed for being electrically connected to The path of electrode and for gas and electrolyte are impermeable.

The gas sensor of the printing of 19. claim 1, the wherein electrolyte include ionic liquid at room temperature, ionomer, contain Water saline solution, alkali or acid solution or sulphuric acid.

The gas sensor of the printing of 20. claim 1, the wherein electrolyte comprising can change into liquid when steam is exposed to The drying material of electrolyte.

The gas sensor of the printing of 21. claim 1, the wherein electrolyte and one or more electrode contacts be thus Electrochemical reaction between the electrolyte, one or more electrodes and object gas provides position.

The gas sensor of the printing of 22. claim 1, wherein one or more electrodes of the electrolyte and this are being more than or equal to 70 ° of contact angular contact.

The gas sensor of the printing of 23. claim 1, wherein one or more electrodes of the electrolyte and this are being more than or equal to 115 ° of contact angular contact.

The gas sensor of the printing of 24. claim 1, also comprising the filter assemblies for being connected to the first local porous substrate, The filter assemblies are included：

Charging port layer comprising one or more filtration holes；With

The filtrate chamber ring of the charging port layer is connected to, the filtrate chamber ring includes the filter material being placed in the filtrate chamber ring Expect and cover one or more gas inlet areas of the first local porous substrate.

The gas sensor of the printing of 25. claim 1, also comprising the container assemblies for being connected to the encapsulated layer, the container assemblies Comprising：

The vessel filling mouth layer of hole is overflowed comprising one or more containers；

It is connected to the vessel filling mouth layer and the encapsulated layer and placement container cavity ring between；With

The vessel filling mouth layer container stopper relative with the container cavity ring is connected to, the wherein container stopper airtightly seals the appearance The container of device charging port layer overflows hole.

The volume capacity of the gas sensor of the printing of 26. claim 25, the wherein container assemblies is electrolysis in the encapsulated layer The about three times of the volume capacity of matter are to about six times.

The volume capacity of the gas sensor of the printing of 27. claim 25, the wherein container assemblies is electrolysis in the encapsulated layer About the one of the volume capacity of matter is again to about 1.1 times.

The gas sensor of the printing of 28. claim 25, the wherein encapsulated layer also include container and the wherein body of the container Product capacity is the about three times of the volume capacity of electrolyte in the encapsulated layer to about six times.

The gas sensor of the printing of 29. claim 25, the wherein encapsulated layer also include container and the wherein body of the container Product capacity is the volume capacity of electrolyte in the encapsulated layer about one again to about 1.1 times.

The gas sensor of the printing of 30. claim 1, wherein the gas that the printing is manufactured in extendible manufacturing process is passed Sensor, the extendible manufacturing process manufacture multiple printings in being configured to the gas sensor sheet material of one or more printings Gas sensor.

The size of the gas sensor of the printing of 31. claim 1, wherein one or more gas inlet areas and this Or multiple electrodes size it is directly related cause larger and/or more gas inlet area corresponding to it is larger and/or compared with Many electrodes.

The size Jing size adjusting of the gas sensor of the printing of 32. claim 31, wherein one or more electrodes is making Background noise is minimized.

The size Jing size adjusting of the gas sensor of the printing of 33. claim 31, wherein one or more electrodes with should The peak signal density of the gas sensor of printing is relevant.

The gas sensor of 34. printings, which includes：

Solid substrate comprising one or more gas inlet areas；

The runner of one or more printings on the solid substrate；

Thus the encapsulating housing for being connected to the solid substrate forms electrolyte cavity between the encapsulating housing and the solid substrate；

The electrolyte being contained in the encapsulating housing；With

One or more electrodes being printed on the solid substrate in the electrolyte cavity, wherein printed with catalyst ink this one The conductive runner telecommunication that individual or multiple electrodes and one or more electrodes are printed with one or more.

The gas sensor of the printing of 35. claim 34, the wherein solid substrate comprising polycarbonate substrate, PET base material or Its combination.

The gas sensor of the printing of 36. claim 34, the wherein encapsulating housing comprising polycarbonate substrate, PET base material or Its combination.

The gas sensor of the printing of 37. claim 34, wherein in deformation point and the encapsulating housing less than the solid substrate Deformation point at a temperature of, the catalyst ink of one or more electrodes is curable.

The gas sensor of the printing of 38. claim 34, wherein the catalyst ink is printed with catalyst ink suspension, the catalysis Agent ink suspension is included：

Comprising following mixture：

The Pt of about 75-79%；

The graphitic carbon of about 8-9%；With

The polypropylene powder of the drying of about 15-17%；With

3mL ethyl cellulose solutions.

The gas sensor of the printing of 39. claim 38, the wherein ethyl cellulose solution also include capryl alcohol.

The gas sensor of the printing of 40. claim 34, wherein use including that sonicated, dispersion and stable technique should Catalyst ink is printed to the solid substrate.

The gas sensor of the printing of 41. claim 34, wherein one or more gas inlet areas include hole.

The gas sensor of the printing of 42. claim 34, the wherein solid substrate are partly coated with polyimides and cause this One or more gas inlet areas of one or more uncoated areas of solid substrate comprising the solid substrate.

The size of the gas sensor of the printing of 43. claim 34, wherein one or more gas inlet areas and this one The size of individual or multiple electrodes is directly related cause larger and/or more gas inlet area corresponding to larger and/or More electrode.

The gas sensor of the printing of 44. claim 34, also comprising the filter assemblies for being connected to the solid substrate, the filtration group Part is included：

Charging port layer comprising one or more filtration holes；With

The filtrate chamber ring of the charging port layer is connected to, the filtrate chamber ring includes the filter material being placed in the filtrate chamber ring Expect and cover one or more gas inlet areas of the solid substrate.

The gas sensor of the printing of 45. claim 34, also comprising the container assemblies for being connected to the encapsulating housing, the container group Part is included：

It is connected to the vessel filling mouth layer and the encapsulating housing and container cavity ring positioned there between；With

The volume capacity of the gas sensor of the printing of 46. claim 45, the wherein container assemblies is the volume of the electrolyte The about three times of capacity are to about six times.

The gas sensor of the printing of 47. claim 34, wherein the gas of the printing is manufactured in extendible manufacturing process Sensor, the extendible manufacturing process manufacture the printing in being configured to the gas sensor sheet material of one or more printings Gas sensor.

The gas sensor of the printing of 48. claim 34, the wherein electrolyte comprising can change into liquid when steam is exposed to The drying material of body electrolyte.

The gas sensor of 49. printings, which includes：

Base material on high temperature with one or more gas inlet areas；

Base material under high temperature；

Be placed on the high temperature under base material and the high temperature between base material and the two is connected to so as to therebetween form electrolyte cavity One or more sealing member spacers；

The electrolyte being contained in the electrolyte cavity；

It is placed in the electrolyte cavity and is printed on base material on the high temperature and/or one or more electrodes on lower base material；

Wherein on the high temperature, base material and base material under the high temperature can sustain at least 260 DEG C of temperature.

On the gas sensor of the printing of 50. claim 49, the wherein high temperature, base material and base material under the high temperature include PTFE, gather Acid imide, Kapton, PEN, polyvinylpyrrolidone its combination.

The gas sensor of the printing of 51. claim 49, also comprising the filter assemblies for being connected to base material on the high temperature, the filtration Component is included：

Charging port layer comprising one or more filtration holes；With

The filtrate chamber ring of the charging port layer is connected to, the filtrate chamber ring includes the filter material being placed in the filtrate chamber ring Expect and cover one or more gas inlet areas of base material on the high temperature.

The gas sensor of the printing of 52. claim 49, also comprising the container assemblies for being connected to base material under the high temperature, the container Component is included：

It is connected to base material and placement container cavity ring between under the vessel filling mouth layer and the high temperature；With

The volume capacity of the gas sensor of the printing of 53. claim 52, the wherein container assemblies is the electrolyte cavity The about three times of volume capacity are to about six times.

The gas sensor of the printing of 54. claim 49, wherein the gas of the printing is manufactured in extendible manufacturing process Sensor, the extendible manufacturing process manufacture printing in being configured to the gas sensor sheet material of one or more printings Gas sensor.

The gas sensor of the printing of 55. claim 49, the wherein electrolyte comprising can change into liquid when steam is exposed to The drying material of body electrolyte.

The size of the gas sensor of the printing of 56. claim 55, wherein one or more gas inlet areas and this one The size of individual or multiple electrodes is directly related cause larger and/or more gas inlet area corresponding to larger and/or More electrode.

The catalyst ink compositionss of 57. gas sensors electrodes for being used for printing, which includes：

Comprising following mixture：

The Pt of about 67-79%；

The graphitic carbon of about 5-15%；With

In the polypropylene powder of the PTFE powder of about 22-24%, about 15-17%, and the polyethylene powders of about 15-17% one Person；With

3mL ethyl cellulose solutions.

The catalyst ink compositionss of 58. claim 57, the wherein PTFE powder include about 0.1 μm to about 5 μm of particle diameter.

The catalyst ink compositionss of 59. claim 57, the wherein polypropylene powder are straight comprising about 0.1 μm to about 5 μm of granule Footpath.

The catalyst ink compositionss of 60. claim 57, the wherein polyethylene powders are straight comprising about 0.2 μm to about 4 μm of granule Footpath.