CN109239132A - A kind of concentration sensor and detection method for direct methanol fuel cell system - Google Patents

A kind of concentration sensor and detection method for direct methanol fuel cell system Download PDF

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CN109239132A
CN109239132A CN201811380539.9A CN201811380539A CN109239132A CN 109239132 A CN109239132 A CN 109239132A CN 201811380539 A CN201811380539 A CN 201811380539A CN 109239132 A CN109239132 A CN 109239132A
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concentration
methanol
pile
sensor
temperature
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CN109239132B (en
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汪晔
魏伟
孙公权
李山
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Shanghai Alcohol Energy Technology Co Ltd
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Shanghai Alcohol Energy Technology Co Ltd
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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Abstract

The invention discloses a kind of concentration sensor and detection method for direct methanol fuel cell system, feature be include shell, temperature sensor and interdigital electrode;Enclosure interior is in hollow cavity, sets in hollow cavity and is divided into the two-part shelf layer that is connected, and two liquid-passing holes are set on shell, and two liquid-passing holes are set to ipsilateral or are connected to on side body with hollow cavity;Temperature sensor and interdigital electrode are fixed in hollow cavity;Interdigital electrode include substrate and in substrate conduction it is interdigital;Conductive interdigital surface platinum plating;In interdigital electrode adjacent conductive it is interdigital between clearance distance and conductive prong finger widths be setting ratio, will concentration sensor access flow path in detect methanol concentration.It, can be in flexible access direct methanol fuel cell flow path, to methanol concentration real-time detection it is an advantage of the invention that the concentration sensor is small in size, structure is simple.

Description

A kind of concentration sensor and detection method for direct methanol fuel cell system
Technical field
The invention belongs to methanol concentration sensor technical fields, more particularly to one kind to be used for direct methanol fuel cell system Concentration sensor and application the concentration sensor detection direct methanol fuel cell system methanol concentration method.
Background technique
Direct alcohol fuel cell (DAFC) is directly to turn the chemical energy being stored in alcohols (methanol, ethyl alcohol etc.) fuel It is melted into the device of electric energy, has the characteristics that specific energy is high, pollution-free, radiationless, easy to carry, safe and reliable, in mobile power source Etc. have broad application prospects.Specific energy height is one of considerable advantage of DAFC, such as the theoretical specific energy of methanol reaches To 6,000Wh/kg or more.Energy density can be greatlyd improve using neat liquid fuel-feed, but due to alcohols (especially first Alcohol) cathode can be penetrated by proton exchange membrane, cause battery performance to reduce, therefore mostly use the aqueous solution of low concentration at present For fuel.From the point of view of state-of-the art, pure fuel can be still carried, is only needed before entering battery pack by fuel concentration It is adjusted to predetermined concentration.Therefore the sensor that alcohol concentration can be measured becomes the Primary Component of DAFC system.
The sensor for being applicable in alcohols detection mostly uses greatly the mode of feulcell prototype.The sensor is similar to a fuel electricity Chi Danchi.Because its material structure is much like with DAFC membrane electrode, there is advantage in terms of industrialization.Wherein, constant electricity is worked in The drive mode sensor of pressure has response signal strong, and concentration range is wide, the advantages such as service life length.Its working principle is that: in film electricity Apply the constant potential that can make methanol that electrochemical oxidation reactions occur on the anode of polar set body (MEA).Methanol solution can be with Anode catalyst layer is directly reached by anode feed, can also be fed by cathode, reaches anode through proton exchange membrane.No matter which Kind mode will be loaded with the electrode surface generation electrochemical oxidation of the noble metal catalysts such as Pt by reaching after appropriate barrier layer. Limiting diffusion current is generated due to there is barrier layer, methanol concentration can be measured by measuring the limiting diffusion current.MEA Oxidation reaction occurs for anode-side methanol, and MEA cathode side generates hydrogen.Form dynamic hydrogen reference electrode.
Anode: CH3OH+H2O-6e-> CO2+6H+
Cathode: 6H++6e-> 3H2
Document 1, (Barton, J.Electrochem.Soc., 145 (1998), 3783) report a kind of logical based on methanol Cross the sensor of dielectric film infiltration.Measuring principle is based on drive mode: alcohols is flowed through from MEA cathode side, and a small amount of alcohol passes through Dielectric film is diffused into anode, and in anode electrochemical oxidation occurs for methanol.Cathode has hydrogen to generate to form Quasi dynamic hydrogen reference electricity Pole.For the interference cleaned anode He prevent oxygen in air, anode chamber is constantly passed through inert gas (such as nitrogen).
Document 2, (patent WO0246733) utilize the saturating alcohol characteristic of film, and it is dense to reach measurement alcohols by measuring its extreme current The purpose of degree.It is proposed a kind of structure of cathode charging.In order to avoid the interference of oxygen in air, which makes anode be in closing State.
Document 3, (United States Patent (USP) US6,306,285B1) report a kind of immersion methanol sensor.Its measuring principle is: The two sides MEA are all immersed in methanol solution.Under externally-applied potential electrochemical oxidation occurs for the methanol for being diffused into anode catalyst layer Reaction occurs reduction in the other side and generates hydrogen.Reinforce barrier layer in anode-side (if densely Toray carbon paper is as diffusion layer) Make to form limit diffusion.Achieve the purpose that measure alcohol concentration by the measurement to carrying current.
Although approach described above can achieve the purpose that measure alcohol concentration, in the side such as stability, measurement range Face all Shortcomings.Using the Methanol permeability of dielectric film, in catalyst layer electrochemical oxidation occurs for the methanol for being diffused into anode Effect, inevitable part methanol can be diffused into the positions such as diffusion layer or even afflux flow field formed it is secondary diffusion cause to measure Inaccuracy.The way that document 1 proposes is to be passed through the inert gases such as nitrogen to be purged.This certainly will make system become it is complicated so that It is difficult to realize.Although the structure that document 2 proposes overcomes the interference of oxygen in air, but still the accumulation that there are methanol in flow field With secondary diffusion problem.Secondary diffusion problem is not present in the structure that document 3 proposes, but since MEA cathode side is to be immersed in alcohols In solution, alcohols inevitably passes through dielectric film and spreads to anode-side, is formed and is interfered to measurement result.In addition the structure by In anode feed, easily there is concentration saturated phenomenon.Although the above method can measure methanol concentration from principle, each comfortable real There is a problem of in the application of border obvious.
Chinese patent application, application number 200510126491.5, applying date 2005.12.14, authorized announcement date 2008 10 Disclosed a kind of alcohol concentration biography for direct alcohol fuel cell system by the moon 22, Authorization Notice No. CN100427945C Sensor forms double MEA (membrane electrode assembly) structures as sensor by folder anode collector among two same MEA components Core component;MEA structure of the present invention does not need additional inert fluid cleaning sun due to making anode be in centre using symmetrical structure Pole.While widening measurement range compared with single MEA structure, sensitivity, stability are improved.Single MEA component cathode plane The long-pending non-structure that piles for being 1: 1-10 with annode area ratio can be with the current density of relative reduction anode.The concentration for weakening anode is full With.In addition, the structure of compound MEA makes flexible access of the sensor in flow path, it is suitble to the real-time detection of alcohol concentration in flow path. But a disadvantage is that MEA structure and unstable, influences, state is to alcohol concentration test result vulnerable to dry and wet state, adion It is affected.
Summary of the invention
In order to overcome the deficiencies of the prior art, the purpose of the present invention is to provide one kind to be used for direct methanol fuel cell system Concentration sensor and detection method, the concentration sensor is small in size, structure is simple, can flexible access direct methanol fuel cell In flow path, the sensitivity and stability of signal response are improved using interdigitated electrode structure, and utilize and be covered in platinum plating conductive prong It is linear accordingly to current signal that the diffusion mass transfer effect of perfluorinated sulfonic resin on finger improves temperature;It is sensed using the concentration The method that device detects the methanol concentration of direct methanol fuel cell system detects methanol concentration in direct methanol fuel cell system Method it is simple, easily operated, be suitble to flow path in methanol concentration real-time detection, make fuel cell system can stablize fortune Row.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of concentration sensor for direct methanol fuel cell system, its main feature is that include shell, for measure into Enter the temperature sensor and interdigital electrode of temperature at the temperature or pile fuel outlet of pile methanol;The enclosure interior is in hollow Cavity sets shelf layer in the hollow cavity, and hollow cavity is separated into the two parts being connected, two are set on the shell For the liquid-passing hole of methanol solution disengaging, two liquid-passing holes are set to ipsilateral or are connected to on side body with hollow cavity;The temperature Sensor and interdigital electrode are set in hollow cavity, and interdigital electrode and temperature sensor stick at branch using epoxy glue or dichloroethanes Rack-layer is ipsilateral or two sides;The interdigital electrode include substrate and in substrate conduction it is interdigital;The conduction interdigital surface plating Platinum;In the interdigital electrode adjacent conductive it is interdigital between clearance distance and conductive prong finger widths be setting ratio, concentration is passed Methanol concentration is detected in sensor access flow path.
Further, the substrate selects one of polyethylene terephthalate, polyimides, epoxy resin material Material production.
Further, the area of the interdigital electrode is 4 × 10-3~1 × 10-2m2
Further, perfluorinated sulfonic resin is covered in the conductive interdigital surface, is passed using the diffusion of perfluorinated sulfonic resin It is linear accordingly to current signal that matter effect improves temperature.
Further, the perfluorinated sulfonic resin is 0.1~12mg/cm in the covering specification of conductive interdigital surface2
Further, the interdigital electrode adjacent conductive it is interdigital between clearance distance and conductive prong finger widths setting ratio Value is 1: 0.2~5;In specific application interdigital electrode adjacent conductive it is interdigital between clearance distance and conductive prong finger widths set Definite value is 50 μm: 100 μm, 50 μm: 50 μm or 100 μm: 50 μm.
Methanol concentration in above-mentioned concentration sensor detection direct methanol fuel cell system is utilized the present invention also provides a kind of Method, the fuel cell system include pile and adjust fuel supply Fuel Control System, the Fuel Control System Equipped with the methanol concentration set point for operation, the concentration sensor is connect with Fuel Control System, its main feature is that including such as Lower step: the measurement of methanol concentration standard value, the concentration and determination that pile inlet and outlet methanol is determined by measurement temperature The methanol concentration being conditioned, the specific steps are as follows:
S1 applies predeterminated voltage at the interdigital electrode both ends, and predeterminated voltage is 0.6~1.2V constant voltage, described dense Methanol solution heat temperature raising is measured interdigital electrode two by the methanol solution that 3~5 normal concentrations are each led into degree sensor It holds electric current and generates electric current and vary with temperature standard curve;
Two concentration sensors are respectively connected at fuel cell pile entrance and exit by S2 in a serial fashion, are surveyed respectively Interdigital electrode both ends electric current is measured, the temperature that the temperature sensor record on concentration sensor passes through the methanol solution of concentration sensor Degree, voltage when measurement in interdigital electrode are predeterminated voltage;
The temperature measured, current data are compared with the temperature of each normal concentration methanol solution, current value, determine pile The concentration of inlet and pile exit methanol;
S3 determines the size relation of pile inlet methanol concentration Yu the methanol concentration set point, and it is dense to adjust methanol Degree is to meeting pile service requirement;
In the case where pile inlet methanol concentration is less than the methanol concentration set point, Fuel Control System increases Refuelling supply, improves methanol concentration;
In the case where pile inlet methanol concentration is greater than the methanol concentration set point, pile exit is determined Whether methanol concentration is less than the methanol concentration set point to generate positive or negative offset concentration;The positive or negative offset is dense Degree is added to pile inlet methanol concentration to generate the methanol concentration being conditioned;By the methanol concentration being conditioned with The methanol concentration set point compares;And lead to if the methanol concentration being conditioned is less than the methanol concentration set point It crosses Fuel Control System and increases fuel supply, improve methanol concentration, and if the methanol concentration being conditioned is greater than the first Determining alcohol set point then reduces fuel supply by Fuel Control System, reduces methanol concentration.
The present invention also provides another to utilize methanol in above-mentioned concentration sensor detection direct methanol fuel cell system The method of concentration, the fuel cell system includes pile and the Fuel Control System for adjusting fuel supply, into the pile Methanol solution flow be setting value, the Fuel Control System be adjusted methanol feedstock quality, the concentration sensor with fire Expect control system connection, its main feature is that, include the following steps: the measurement of methanol concentration standard value, electricity is determined by measurement temperature The concentration of heap inlet and outlet methanol and determining methanol inlet amount, the specific steps are as follows:
A1 applies predeterminated voltage at the interdigital electrode both ends, and predeterminated voltage is 0.6~1.2V constant voltage, described dense Methanol solution heat temperature raising is measured interdigital electrode two by the methanol solution that 3~5 normal concentrations are each led into degree sensor It holds electric current and generates electric current and vary with temperature standard curve;
Two concentration sensors are respectively connected at fuel cell pile entrance and exit by A2 in a serial fashion, are first measured Pile inlet concentration sensor interdigital electrode both ends electric current, the temperature sensor record on concentration sensor pass through pile entrance Locate the temperature of the methanol solution of concentration sensor;
After a period of time of setting, pile exit concentration sensor interdigital electrode both ends electric current is measured, concentration passes The temperature that temperature sensor record on sensor passes through the methanol solution of pile exit concentration sensor;One section of the setting Time is 10s~1min;
Voltage when measurement in interdigital electrode is predeterminated voltage;
The temperature measured, current data are compared with the temperature of each normal concentration methanol solution, current value, determine pile The concentration of inlet and pile exit methanol;
The difference of the methanol concentration in pile exit and the methanol concentration of pile entrance described in A3 and the methanol solution The product of flow is the amount of the methanol of pile consumption in the time of above-mentioned setting, when next section of setting time starts, by described Fuel Control System supplies the amount of the methanol of above-mentioned consumption.
Compared with prior art, it is an advantage of the invention that the concentration sensor is small in size, structure is simple, can flexible access it is straight It connects in methanol fuel cell flow path, the sensitivity and stability of signal response is improved using interdigitated electrode structure, and utilize and cover Be placed on platinum plating it is conductive it is interdigital on the diffusion mass transfer effect of perfluorinated sulfonic resin to improve temperature linear accordingly to current signal; The method for detecting methanol concentration in direct methanol fuel cell system is simple, easily operated, is suitble to methanol concentration in flow path Real-time detection, make fuel cell system being capable of stable operation.
Detailed description of the invention
The present invention will be further described with reference to the accompanying drawing.
Fig. 1 is concentration sensor structural schematic diagram of the present invention.
Fig. 2 is interdigitated electrode structure schematic diagram of the present invention.
Fig. 3 is 50 μm: 50 μm of interdigital electrode concentration sensors of the invention in 0.3M, 0.5M, 0.8M, 1.0M methanol solution Electric current and temperature relation schematic diagram.
Fig. 4 be 50 μm: 100 μm of the present invention, 50 μm: 50 μm, 100 μm: 50 μm of interdigital electrode concentration sensors are in 0.5M first Electric current and temperature relation schematic diagram in alcoholic solution.
Fig. 5 is that the embodiment of the present invention 3 is a kind of dense using methanol in concentration sensor detection direct methanol fuel cell system The method logical flow chart of degree.
In figure: 1- shell 2- temperature sensor 3- interdigital electrode 4- hollow cavity 5- liquid-passing hole 6- shelf layer 7- base Bottom 8- conduction is interdigital.
Specific embodiment
The present invention will be further described combined with specific embodiments below.
Embodiment 1
As shown in Figure 1 and Figure 2, a kind of concentration sensor for direct methanol fuel cell system, its main feature is that including shell Body 1, temperature sensor 2 and interdigital electrode 3 for measuring the temperature or temperature at pile fuel outlet that enter pile methanol;Shell It is in hollow cavity 4 inside body 1, sets shelf layer 6 in the hollow cavity 4, hollow cavity 4 is separated into two to be connected Point, set two liquid-passing holes 5 for methanol solution disengaging on shell 1, two liquid-passing holes 5 be set to it is ipsilateral or on side body with it is hollow Cavity 4 is connected to;Temperature sensor 2 and interdigital electrode 3 are set in hollow cavity, and interdigital electrode 3 and temperature sensor 2 are fixed on branch Rack-layer 6 is ipsilateral or two sides, can be used epoxy glue or dichloroethanes as bonding agent when fixed;Interdigital electrode 3 includes substrate 7 and sets In the conduction interdigital 8 in substrate 7;Conductive interdigital 8 surface platinum plating;In interdigital electrode 3 adjacent conductive it is interdigital between clearance distance It is setting ratio with conductive prong finger widths, concentration sensor is accessed in flow path and detects methanol concentration.
Substrate 7 selects the material production of one of polyethylene terephthalate, polyimides, epoxy resin.It is interdigital The area of electrode 3 is 4 × 10-3~1 × 10-2m2.Perfluorinated sulfonic resin is covered on conductive interdigital 8 surface, utilizes perfluorinated sulfonic acid tree It is linear accordingly to current signal that the diffusion mass transfer effect of rouge improves temperature.
Perfluorinated sulfonic resin is 0.1~12mg/cm in the covering specification of conductive interdigital surface2
Clearance distance between 3 adjacent conductive of interdigital electrode interdigital 8 and conductive prong finger widths set ratio as 1: 0.2~ 5;In specific application 8 adjacent conductive of interdigital electrode it is interdigital between clearance distance and conductive prong finger widths setting value be 50 μm : 100 μm, 50 μm: 50 μm or 100 μm: 50 μm.
Embodiment 2
Concentration sensor in above-described embodiment is applied to be respectively adopted 0.3M, 0.5M, 0.8M, 1.0M methanol solution into The direct methanol fuel cell system of material applies 0.8V constant voltage, the methanol that heating passes through concentration sensor to interdigital electrode Solution records the temperature of interdigital electrode two sides electric current and temperature sensor measurement, obtains electric current and temperature relation as shown in Figure 3, Influence of the temperature to current-responsive has preferable linear as shown in Figure 3.It therefore, will in the work of direct methanol fuel cell pile Concentration sensor of the invention is connect with Fuel Control System, by the detection to temperature and electric current, available methanol it is dense Range is spent, so that feed quantity is adjusted to methanol pump input signal to Fuel Control System, to make the methanol solution into pile It is maintained at optium concentration.
Interdigital electrode concentration sensor is put into 0.5M methanol solution, electric current and temperature relation are measured, as shown in figure 4, By adjusting adjacent conductive it is interdigital between clearance distance and the setting values of conductive prong finger widths be 50 μm: 100 μm, 50 μm: 50 μm, 100 μm: 50 μm can be obtained unlike signal response intensity, and since interdigital electrode area is bigger, platinum plating amount is higher, cost Also higher, but signal respective strengths are bigger, thus adjacent conductive it is interdigital between clearance distance and conductive prong finger widths Setting value difference causes the performance difference of concentration sensor, can be selected according to different direct methanol fuel cell systems.
Embodiment 3
Methanol concentration in above-mentioned concentration sensor detection direct methanol fuel cell system is utilized the present invention also provides a kind of Method, fuel cell system include pile and adjust fuel supply Fuel Control System, Fuel Control System be equipped be used for The methanol concentration set point of operation, concentration sensor are connect with Fuel Control System, as shown in figure 5, its main feature is that including as follows Step: the measurement of methanol concentration standard value is determined the concentration of pile inlet and outlet methanol by measurement temperature and determines quilt The methanol concentration of adjusting, the specific steps are as follows:
S1 applies predeterminated voltage at interdigital electrode both ends, and predeterminated voltage is 0.6~1.2V constant voltage, in concentration sensor In each lead into the methanol solutions of 3~5 normal concentrations, by methanol solution heat temperature raising, measure interdigital electrode both ends electric current simultaneously It generates electric current and varies with temperature standard curve;
Two concentration sensors are respectively connected at fuel cell pile entrance and exit by S2 in a serial fashion, are surveyed respectively Interdigital electrode both ends electric current is measured, the temperature that the temperature sensor record on concentration sensor passes through the methanol solution of concentration sensor Degree, voltage when measurement in interdigital electrode are predeterminated voltage;
The temperature measured, current data are compared with the temperature of each normal concentration methanol solution, current value, determine pile The concentration of inlet and pile exit methanol;
S3 determines the size relation of pile inlet methanol concentration Yu the methanol concentration set point, adjust methanol concentration to Meet pile service requirement;
In the case where pile inlet methanol concentration is less than the methanol concentration set point, Fuel Control System increases combustion Material supply, improves methanol concentration;
In the case where pile inlet methanol concentration is greater than the methanol concentration set point, pile exit methanol is determined Whether concentration is less than the methanol concentration set point to generate positive or negative offset concentration;Positive or negative offset concentration is added to Pile inlet methanol concentration is to generate the methanol concentration being conditioned;The methanol concentration being conditioned and the methanol concentration are set Point compares;And increased if the methanol concentration being conditioned is less than the methanol concentration set point by Fuel Control System Refuelling supply improves methanol concentration, and passes through combustion if the methanol concentration being conditioned is greater than the methanol concentration set point Expect that control system reduces fuel supply, reduces methanol concentration.
Embodiment 4
The present invention also provides another to utilize methanol in above-mentioned concentration sensor detection direct methanol fuel cell system The method of concentration, fuel cell system include pile and the Fuel Control System for adjusting fuel supply, and the methanol into pile is molten Flow quantity is setting value, and methanol feedstock quality is adjusted in Fuel Control System, and concentration sensor is connect with Fuel Control System, Feature is to include the following steps: the measurement of methanol concentration standard value, determine pile inlet and outlet methanol by measurement temperature Concentration and determine methanol inlet amount, the specific steps are as follows:
A1 applies predeterminated voltage at interdigital electrode both ends, and predeterminated voltage is 0.6~1.2V constant voltage, in concentration sensor In each lead into the methanol solutions of 3~5 normal concentrations, by methanol solution heat temperature raising, measure interdigital electrode both ends electric current simultaneously It generates electric current and varies with temperature standard curve;
Two concentration sensors are respectively connected at fuel cell pile entrance and exit by A2 in a serial fashion, are first measured Pile inlet concentration sensor interdigital electrode both ends electric current, the temperature sensor record on concentration sensor pass through pile entrance Locate the temperature of the methanol solution of concentration sensor;
After a period of time of setting, pile exit concentration sensor interdigital electrode both ends electric current is measured, concentration passes The temperature that temperature sensor record on sensor passes through the methanol solution of pile exit concentration sensor;A period of time of setting For 10s~1min;
Voltage when measurement in interdigital electrode is predeterminated voltage;
The temperature measured, current data are compared with the temperature of each normal concentration methanol solution, current value, determine pile The concentration of inlet and pile exit methanol;
The difference of the methanol concentration of the methanol concentration and pile entrance in A3 pile exit and the methanol solution flow Product be above-mentioned setting time in pile consumption methanol amount, when next section of setting time starts, by the fuel Control system supplies the amount of the methanol of above-mentioned consumption.

Claims (9)

1. a kind of concentration sensor for direct methanol fuel cell system, it is characterised in that: including shell, temperature sensor And interdigital electrode;The enclosure interior is in hollow cavity, and shelf layer is set in the hollow cavity, two confessions are set on the shell The liquid-passing hole of methanol solution disengaging, two liquid-passing holes are set to ipsilateral or are connected to on side body with hollow cavity;The temperature passes Sensor and interdigital electrode are set in hollow cavity, are fixed on that shelf layer is ipsilateral or two sides;The interdigital electrode includes substrate and sets It is interdigital in the conduction in substrate;The conduction interdigital surface platinum plating;In the interdigital electrode adjacent conductive it is interdigital between gap Distance is setting ratio with conductive prong finger widths.
2. a kind of concentration sensor for direct methanol fuel cell system according to claim 1, it is characterised in that: institute The material for stating substrate is one of polyethylene terephthalate, polyimides or epoxy resin.
3. a kind of concentration sensor for direct methanol fuel cell system according to claim 1, it is characterised in that: institute The area for stating interdigital electrode is 4 × 10-3~1 × 10-2m2
4. a kind of concentration sensor for direct methanol fuel cell system according to claim 3, it is characterised in that: institute It states and covers perfluorinated sulfonic resin in conductive interdigital surface.
5. a kind of concentration sensor for direct methanol fuel cell system according to claim 4, it is characterised in that: institute It is 0.1~12mg/cm that perfluorinated sulfonic resin, which is stated, in the covering specification of conductive interdigital surface2
6. a kind of concentration sensor for direct methanol fuel cell system according to claim 5, it is characterised in that: institute State interdigital electrode adjacent conductive it is interdigital between clearance distance and conductive prong finger widths set ratio as 1: 0.2~5.
7. a kind of be used to detect direct methanol fuel using concentration sensor described in claim 1~6 Arbitrary Term claim The method of methanol concentration in battery system, the fuel cell system include pile and the fuel control system for adjusting fuel supply System, the Fuel Control System are equipped with the methanol concentration set point for operation, the concentration sensor and Fuel Control System Connection, which comprises the steps of: methanol concentration standard value measurement, by measurement temperature come determine pile import and The concentration of exit methanol and the determining methanol concentration being conditioned, the specific steps are as follows:
S1 applies predeterminated voltage at the interdigital electrode both ends, and predeterminated voltage is 0.6~1.2V constant voltage, passes in the concentration Methanol solution heat temperature raising is measured interdigital electrode both ends electricity by the methanol solution that 3~5 normal concentrations are each led into sensor It flows and generates electric current and vary with temperature standard curve;
Two concentration sensors are respectively connected at fuel cell pile entrance and exit by S2 in a serial fashion, respectively measurement fork Refer to electrode both ends electric current, the temperature sensor record on concentration sensor is surveyed by the temperature of the methanol solution of concentration sensor Voltage when amount in interdigital electrode is predeterminated voltage;
The temperature measured, current data are compared with the temperature of each normal concentration methanol solution, current value, determine pile entrance The concentration at place and pile exit methanol;
S3 determines the size relation of pile inlet methanol concentration Yu the methanol concentration set point, adjust methanol concentration to Meet pile service requirement;
In the case where pile inlet methanol concentration is less than the methanol concentration set point, Fuel Control System increases combustion Material supply, improves methanol concentration;
In the case where pile inlet methanol concentration is greater than the methanol concentration set point, pile exit methanol is determined Whether concentration is less than the methanol concentration set point to generate positive or negative offset concentration;The positive or negative offset concentration is added Pile inlet methanol concentration is added to generate the methanol concentration being conditioned;By the methanol concentration being conditioned with it is described Methanol concentration set point compares;And pass through combustion if the methanol concentration being conditioned is less than the methanol concentration set point Expect that control system increases fuel supply, improves methanol concentration, and if the methanol concentration being conditioned is dense greater than the methanol It spends set point and fuel supply is then reduced by Fuel Control System, reduce methanol concentration.
8. a kind of be used to detect direct methanol fuel using concentration sensor described in claim 1~6 Arbitrary Term claim The method of methanol concentration in battery system, the fuel cell system include pile and the fuel control system for adjusting fuel supply System, the methanol solution flow into the pile is setting value, and methanol feedstock quality is adjusted in the Fuel Control System, described Concentration sensor is connect with Fuel Control System, which comprises the steps of: the measurement of methanol concentration standard value passes through Temperature is measured to determine the concentration of pile inlet and outlet methanol and determine methanol inlet amount, the specific steps are as follows:
A1 applies predeterminated voltage at the interdigital electrode both ends, and predeterminated voltage is 0.6~1.2V constant voltage, passes in the concentration Methanol solution heat temperature raising is measured interdigital electrode both ends electricity by the methanol solution that 3~5 normal concentrations are each led into sensor It flows and generates electric current and vary with temperature standard curve;
Two concentration sensors are respectively connected at fuel cell pile entrance and exit by A2 in a serial fashion, first measure pile Inlet concentration sensor interdigital electrode both ends electric current, the temperature sensor record on concentration sensor are dense by pile inlet Spend the temperature of the methanol solution of sensor;
After a period of time of setting, pile exit concentration sensor interdigital electrode both ends electric current, concentration sensor are measured On the temperature sensor record temperature that passes through the methanol solution of pile exit concentration sensor;
Voltage when measurement in interdigital electrode is predeterminated voltage;
The temperature measured, current data are compared with the temperature of each normal concentration methanol solution, current value, determine pile entrance The concentration at place and pile exit methanol;
The difference of the methanol concentration in pile exit and the methanol concentration of pile entrance described in A3 and the methanol solution flow Product be above-mentioned setting time in pile consumption methanol amount, when next section of setting time starts, by the fuel Control system supplies the amount of the methanol of above-mentioned consumption.
9. according to the method described in claim 8, it is characterized by: a period of time set described in step A2 as 10s~ 1min。
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