CN209247675U - A kind of concentration sensor for direct methanol fuel cell system - Google Patents
A kind of concentration sensor for direct methanol fuel cell system Download PDFInfo
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- CN209247675U CN209247675U CN201821907610.XU CN201821907610U CN209247675U CN 209247675 U CN209247675 U CN 209247675U CN 201821907610 U CN201821907610 U CN 201821907610U CN 209247675 U CN209247675 U CN 209247675U
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Abstract
The utility model discloses a kind of concentration sensor 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 the utility model has the advantages that the concentration sensor is small in size, structure is simple.
Description
Technical field
The utility model belongs to methanol concentration sensor technical field, more particularly to a kind of for direct methanol fuel cell
The concentration sensor of system.
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；It is clear not need additional inert fluid due to making anode be in centre using symmetrical structure for the utility model MEA structure
Clean anode.While widening measurement range compared with single MEA structure, sensitivity, stability are improved.Single MEA component yin
The long-pending non-structure that piles for being 1: 1-10 with annode area ratio of pole-face can be with the current density of relative reduction anode.Weaken the dense of anode
Degree saturation.In addition, the structure of compound MEA makes flexible access of the sensor in flow path, alcohol concentration is real-time in suitable flow path
Detection.But a disadvantage is that MEA structure and unstable, influences, state tests alcohol concentration vulnerable to dry and wet state, adion
As a result it is affected.
Utility model content
In order to overcome the deficiencies of the prior art, the purpose of this utility model is to provide one kind to be used for direct methanol fuel cell
The concentration sensor of system, the concentration sensor is small in size, structure is simple, can flexible access direct methanol fuel cell flow path
In, improve the sensitivity and stability of signal response using interdigitated electrode structure, and using be covered in 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；It is examined using the concentration sensor
The method for surveying the methanol concentration of direct methanol fuel cell system detects the side of methanol concentration in direct methanol fuel cell system
Method is simple, easily operated, is suitble to the real-time detection of methanol concentration in flow path, and make fuel cell system being capable of stable operation.
To achieve the above objectives, the present invention adopts the following technical solutions:
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.
Utilize the method for methanol concentration in above-mentioned concentration sensor detection direct methanol fuel cell system, the fuel electricity
Cell system includes pile and the Fuel Control System for adjusting fuel supply, and the Fuel Control System is equipped with the methanol for operation
Concentration set point, the concentration sensor are connect with Fuel Control System, its main feature is that including the following steps: methanol concentration standard
Value measurement, the concentration that pile inlet and outlet methanol is determined by measurement temperature and the determining methanol concentration being conditioned, tool
Steps are as follows for body:
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.
Compared with prior art, it the utility model has the advantages that the concentration sensor is small in size, structure is simple, can flexibly connect
Enter in direct methanol fuel cell flow path, the sensitivity and stability of signal response, and benefit are improved using interdigitated electrode structure
Be covered in platinum plating it is conductive it is interdigital on the diffusion mass transfer effect of perfluorinated sulfonic resin to improve temperature corresponding to current signal
Linearly；The method for detecting methanol concentration in direct methanol fuel cell system is simple, easily operated, is suitble to methanol in flow path dense
The real-time detection of degree, make fuel cell system being capable of stable operation.
Detailed description of the invention
The utility model is described further with reference to the accompanying drawing.
Fig. 1 is the utility model concentration sensor structural schematic diagram.
Fig. 2 is the utility model interdigitated electrode structure schematic diagram.
Fig. 3 is 50 μm: 50 μm of interdigital electrode concentration sensors of the utility model in 0.3M, 0.5M, 0.8M, and 1.0M methanol is molten
Electric current and temperature relation schematic diagram in liquid.
Fig. 4 be 50 μm: 100 μm of the utility model, 50 μm: 50 μm, 100 μm: 50 μm of interdigital electrode concentration sensors exist
Electric current and temperature relation schematic diagram in 0.5M methanol solution.
Fig. 5, which is that the utility model embodiment 3 is a kind of, utilizes first in concentration sensor detection direct methanol fuel cell system
The method logical flow chart of determining alcohol.
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 utility model is described further 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
The concentration sensor of the utility model is connect with Fuel Control System, by the detection to temperature and electric current, available methanol
Concentration range, so that feed quantity is adjusted to Fuel Control System to methanol pump input signal, to make the methanol into pile
Solution 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
Utilize the method for methanol concentration in above-mentioned concentration sensor detection direct methanol fuel cell system, fuel cell system
System includes pile and the Fuel Control System for adjusting fuel supply, and Fuel Control System is equipped with the methanol concentration setting for operation
Point, concentration sensor are connect with Fuel Control System, as shown in figure 5, its main feature is that including the following steps: methanol concentration standard value
Measurement, the concentration that pile inlet and outlet methanol is determined by measurement temperature and the determining methanol concentration being conditioned, specifically
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.
Claims (6)
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.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109239132A (en) * | 2018-11-20 | 2019-01-18 | 上海醇加能源科技有限公司 | A kind of concentration sensor and detection method for direct methanol fuel cell system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109239132A (en) * | 2018-11-20 | 2019-01-18 | 上海醇加能源科技有限公司 | A kind of concentration sensor and detection method for direct methanol fuel cell system |
| CN109239132B (en) * | 2018-11-20 | 2023-08-08 | 上海醇加能源科技有限公司 | Concentration sensor and detection method for direct methanol fuel cell system |
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