CN108615919A - Passive direct methanol fuel cell system and optimization method - Google Patents
Passive direct methanol fuel cell system and optimization method Download PDFInfo
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- CN108615919A CN108615919A CN201810541069.3A CN201810541069A CN108615919A CN 108615919 A CN108615919 A CN 108615919A CN 201810541069 A CN201810541069 A CN 201810541069A CN 108615919 A CN108615919 A CN 108615919A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
- H01M8/04014—Heat exchange using gaseous fluids; Heat exchange by combustion of reactants
- H01M8/04022—Heating by combustion
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a kind of passive direct methanol fuel cell system and optimization methods, the battery system includes insulation shell, the passive direct methanol fuel cell being arranged in insulation shell and heating part, the methanol intracavitary of the passive direct methanol fuel cell is equipped with the mass transfer barrier layer for being evenly distributed with several through-holes, and the methanol concentration for making the anode plate with cell reaction portion react adapts to cell output.According to battery system proposed by the present invention, the output performance and dynamic response characteristic of passive direct methanol fuel cell system are improved.
Description
Technical field
The present invention relates to methanol fuel cell more particularly to a kind of passive direct methanol fuel cell system and optimization sides
Method.
Background technology
The energy is the power and the essential strategic material of national defense construction of the national economic development.Human society continues
Fast development be unable to do without the innovation and exploitation of strong energy safeguard and advanced new energy technology.The transition of energy resource structure each time
, all can be with the rapid development of productivity with revolution, and push the progress of mankind's military affairs and civilian science and technology.With social productive forces
Horizontal continuous improvement, people gradually recognize that inefficiency the utilization of traditional fossil energy with serious pollution effect, seek
The energy utilization patterns looked for high-energy source utilization ratio, and do not polluted the environment are trends of the times.In this context, fuel electricity
Pool technology is not limited because of its high volume energy density by Carnot cycle, as long as theoretically fuel is infinitely supplied, can realize electricity
The unlimited electric discharge in pond, belongs to the battery capacity of energy conversion device, is increasingly valued by people.In recent years, integrated electronic
Technology, microelectromechanical systems (Micro Electro Mechanical System, MEMS) technology are used widely, micro-
Type weapon system-of-systems develop to integrated, multifunction on direction with portable electronic product, while to its provisioned power supply
More stringent requirements are proposed.Traditional large scale energy resource system can no longer meet the needs of development in science and technology, and have microsize
More concerns of research institution of various countries are increasingly subject to micro- energy technology of high-energy density.The rapid hair of MEMS technology in recent years
It opens up and provides new realization means with making for the processing of micro- energy device.What MEMS technology was combined into fuel cell technology
Micro fuel cell has that energy conversion efficiency is high, high-power continued power ability is strong, environment compared to the micro- energy of other types
Close friend, started quickly at low temperature, reliability is high and is convenient for the advantages that integrated, is novel micro- energy with broad prospect of application
Source.
Micro direct methanol fuel battery (Micro Direct Methanol Fuel Cell, μ DMFC) and other types
Compare, have the characteristics that fuel source is abundant, easy to carry, simple in structure and operating condition is simple, it is preferably become it is small-sized with
The supply system of mobile model power supply.By feeding manner difference, μ DMFC be divided tos for active and two kinds of passive type, with it is active directly
It connects methanol fuel cell to compare, passive direct methanol fuel cell system realizes raw material using the free convection of methanol and air
Supply is not necessarily to the support of auxiliary system, has given up a large amount of attachment device, eliminated the loss of parasitic power, theoretically have
Higher system effectiveness；Again because its is simple in structure, easy to operate, material and operating cost are low, operating status best suit it is miniature just
Take the requirement of formula mobile power.
Since passive type μ DMFC service conditions are simple, working environment is mostly normal temperature and pressure, it is exported Just because of this
Power is faced with prodigious restriction, such as：Optimal operating condition is not achieved in the mass-and heat-transfer of progress spontaneous first, secondly room temperature
The activity of catalyst can be caused fuel availability not high by prodigious inhibition, last methanol crossover phenomenon etc. under normal pressure, these
It is to cause the serious principal element of battery polarization.Ignore the structural factor of passive type μ DMFC, μ DMFC final output power is close
Degree is also influenced by concentration of methanol solution, operating temperature and current density, such as：Influence of the methanol concentration to methanol crossover is most
To be notable, concentration is higher, and the transmission rate of methanol is also higher；Temperature is optimal operating condition and influences the master of catalyst activity
Want index；Current density generates hot close relation with electrochemical reaction, and current density is bigger, and reaction is more violent, reaction life
More at heat, battery body temperature is also higher.And the relationship between this three between output power density is very multiple
Miscellaneous, the performance of battery can be improved by the one hand improving battery operating temperature, such as：(1) catalytic activity for improving anode, accelerates
Electrochemical reaction rates；(2) accelerate reactant mass transfer, improve methanol diffusion coefficient；(3) proton exchange membrane internal resistance is reduced.But
With the raising of operating temperature, methanol crossover rate can increase therewith, and influence of the methanol crossover to methanolica cell can be gradually expanded.
And on the other hand, methanol concentration influences significantly methanol crossover, and methanol concentration is excessively high to cause excessive methanol to wear to make cause
Battery performance seriously reduces, and under the conditions of higher methanol concentration, battery has benefited from exothermic reaction of the methanol in cathode, and reaction is put
The heat gone out can improve the operating temperature of battery again, promote the raising of battery performance.In addition, with the increase of current density, first
The transmission rate of alcohol can decrease.In different current density operations, play a leading role to cell output density
Factor is also not quite similar so that the temperature that battery can obtain optimum performance is also differed with methanol concentration.
Therefore, output performance is in 20mW/cm2 or so under current passive type μ DMFC room temperature, and efficiency is less than 30%.It is practical
The influence that running parameter (concentration of methanol solution, temperature etc.) exports passive type μ DMFC efficiency is also more apparent.Meanwhile μ DMFC
Structure type is single, cannot be injected using pure methanol as fuel.Energy density is relatively low, passive type μ DMFC best methanol when working
Concentration is generally 2M or so, and the control of methanol concentration and battery system temperature is completed by additional equipment mostly, cannot achieve
The autonomous control of battery.
Invention content
The present invention provides the optimization method of a kind of passive direct methanol fuel cell system and battery system, and it is passive to improve
The output performance and dynamic response characteristic of formula direct methanol fuel cell system.
One side according to the present invention provides a kind of passive direct methanol fuel cell system, including insulation shell,
The passive direct methanol fuel cell being arranged in insulation shell and heating part, the passive direct methanol fuel cell
Methanol intracavitary is equipped with the mass transfer barrier layer for being evenly distributed with several through-holes, for making the sun with passive direct methanol fuel cell
The methanol concentration of pole plate reaction adapts to cell output.
Optionally, in battery system of the present invention, the methanol chamber of the passive direct methanol fuel cell includes pure
Methanol chamber and cushion chamber, the mass transfer barrier layer is between pure methanol chamber and cushion chamber.
Optionally, in battery system of the present invention, the heating part is using catalysis combustion heating system, the catalysis combustion
The catalytic combustor for burning heating system is connected by thermostat valve with the methanol chamber of the passive direct methanol fuel cell, described
Thermostat valve is for controlling the break-make that methanol intracavitary methanol flows to catalytic combustor.
Optionally, in battery system of the present invention, the import of the catalytic combustor of the catalysis combustion heating system is also
Equipped with vapour-liquid switch.
Optionally, in battery system of the present invention, the thermostat valve includes valve body, and the shape being arranged in valve body
Memory alloy spring, spool and bias spring, the valve body is interior to be equipped with runner, is offered and runner phase on the side wall of valve body one end
Logical inlet, the spool are arranged at the inlet end of valve body, and the shape memory alloy spring and bias spring distinguish position
In the both sides of spool.
Optionally, in battery system of the present invention, the insulation shell is made of phase-change material.
Optionally, in battery system of the present invention, the first heat pipe, first heat pipe one are equipped in the insulation shell
End extends to catalysis combustion heating system, and in the catalytic combustor of embedded catalysis combustion heating system；The other end extends to institute
State the cathode plate of passive direct methanol fuel cell.
Optionally, in battery system of the present invention, the anode plate and cathode of the passive direct methanol fuel cell
The second heat pipe is both provided in plate, the caliber T value ranges of second heat pipe are as follows：0.4mm≤T≤1mm.
Other side according to the present invention provides a kind of optimization method of passive direct methanol fuel cell system,
Applied to above-mentioned passive direct methanol fuel cell system, include the following steps：
Based on the structure of the passive direct methanol fuel cell system, and combine passive direct methanol fuel cell
Multiple physical field, establish the Dynamic Simulation Model of passive direct methanol fuel cell system, the passive direct methanol combustion
Expect that the Dynamic Simulation Model of battery system includes：Concentration simulation model or/and temperature simulation model；
According to preset condition, the Dynamic Simulation Model of the passive direct methanol fuel cell system is analyzed,
Determine each running parameter in the passive direct methanol fuel cell system.
Optionally, in optimization method of the present invention, the concentration simulation model includes one in following simulation model
Or it is multiple：Mass transfer barrier layer simulation model, methanol chamber simulation model, anode plate simulation model, cathode plate simulation model and film electricity
Pole simulation model；The temperature simulation model includes one or more of following simulation model：It is catalyzed combustion heating system
Catalytic combustor interior flow field simulation model, self-respiration type simulation model, the thermostat valve simulation model for being catalyzed combustion heating system
And insulation shell simulation model.
Beneficial effects of the present invention：Passive direct methanol fuel cell system proposed by the present invention and battery system it is excellent
Change method, methanol concentration, temperature and current density three when taking full advantage of the work of passive direct methanol fuel cell system
Between relationship, achieve the effect that the adaptive of passive direct methanol fuel cell systemic concentration and temperature, the battery made to exist
Under best operating condition, the output performance and dynamic response characteristic of battery are improved.
Above description is only the general introduction of technical solution of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, and in order to allow above and other objects of the present invention, feature and advantage can
It is clearer and more comprehensible, below the special specific implementation mode for lifting the present invention.
Description of the drawings
By reading the detailed description of hereafter preferred embodiment, various other advantages and benefit are common for this field
Technical staff will become clear.Attached drawing only for the purpose of illustrating preferred embodiments, and is not considered as to the present invention
Limitation.And throughout the drawings, the same reference numbers will be used to refer to the same parts.In the accompanying drawings：
Fig. 1 is the structural schematic diagram of first embodiment of the invention；
Fig. 2 is the structural schematic diagram that methanol chamber uses pure methanol chamber and cushion chamber in first embodiment of the invention；
Fig. 3 is enlarged drawing at C in Fig. 1；
Fig. 4 is second embodiment of the invention structural schematic diagram；
Fig. 5 is enlarged drawing at A in Fig. 4；
Fig. 6 is third embodiment of the invention structural schematic diagram；
Fig. 7 is enlarged drawing at B in Fig. 6；
Fig. 8 is the optimization method flow for the passive direct methanol fuel cell system that fourth embodiment of the invention provides
Figure；
Fig. 9 is the fuel cell that provides of fourth embodiment of the invention output power density under different temperatures and concentration conditions
Relational graph；
Figure 10 is the exemplary flow chart of optimization method that fourth embodiment of the invention provides.
Specific implementation mode
The exemplary embodiment of the disclosure is more fully described below with reference to accompanying drawings.Although showing the disclosure in attached drawing
Exemplary embodiment, it being understood, however, that may be realized in various forms the disclosure without should be by embodiments set forth here
It is limited.On the contrary, these embodiments are provided to facilitate a more thoroughly understanding of the present invention, and can be by the scope of the present disclosure
Completely it is communicated to those skilled in the art.
In the first embodiment of the present invention, a kind of passive direct methanol fuel cell system is provided, as shown in Figure 1,
The passive direct methanol fuel cell 2 being arranged in insulation shell 1 including insulation shell 1 and heating part 3, passive type is direct
Methanol fuel cell 2 includes methanol chamber 2-1, anode plate 2-3, cathode plate 2-4, membrane electrode 2-5.
The mass transfer for being evenly distributed with several through-holes is equipped in the methanol chamber 2-1 of the passive direct methanol fuel cell 2
Barrier layer 2-2, the methanol concentration for making to react with the anode plate 2-3 of battery 2 adapt to cell output.The mass transfer barrier layer
2-2 is the mass transfer barrier layer of different size and effective diffusion area, the mass transfer barrier layer of the different size and effective expanding area
Refer to the mass transfer barrier layer of different porosities, different pore size, different materials or different hydrophobe characteristic equal-specification characteristics.The biography
Matter barrier layer is the composite layer being made of base and surface layer, such as：Using polytetrafluoroethylene (PTFE) (PTFE), stainless steel felt, stone
The base material as mass transfer barrier layer such as black plate, PP and PE porous media plastic plates, using close and distant water process, wax solution impregnates
Deng the surface layer for constituting mass transfer barrier layer.The present invention realizes the injection of methanol fuel using the capillary force of mass transfer barrier layer 2-2, and logical
The mass transfer barrier layer for crossing different size adjusts the methanol concentration that anode plate is reached by the through-hole on mass transfer barrier layer, keeps arrival passive
The methanol concentration of the anode plate 2-3 reactions of formula direct methanol fuel cell 2 adapts to cell output.Passive type of the present invention is direct
Methanol solution is true according to concentration of methanol solution, temperature and current density triadic relation in the methanol chamber 2-1 of methanol fuel cell 2
Fixed different methanol concentrations can also be pure methanol.The passive direct methanol fuel cell 2 includes that passive miniature is direct
Methanol fuel cell, interior are equipped with of the methanol chamber 2-1 of passive miniature direct methanol fuel cell are evenly distributed with several through-holes
Mass transfer barrier layer 2-2.
Optionally, shown in Figure 2 in the embodiment of the present invention, the methanol chamber of the passive direct methanol fuel cell
Including pure methanol chamber 2-1-1 and cushion chamber 2-1-2, pure methanol chamber 2-1-1 for improving fuel battery energy amount efficiency, increase electric discharge
Time.Cushion chamber 2-1-2 damages membrane electrode for avoiding M100 fuel from being in direct contact cell reaction region.The mass transfer resistance
Barrier 2-2 is between pure methanol chamber 2-1-1 and cushion chamber 2-1-2.By increasing difference between pure methanol chamber and cushion chamber
Methanol in cushion chamber 2-1-2 is realized in the mass transfer barrier layer of specification and effective diffusion area using the capillary force of mass transfer barrier layer 2-2
Constant concentration.
Shown in Figure 3, membrane electrode 2-5 includes anode and cathode diffusion layer 2-5-1, anode and cathode Catalytic Layer 2-5-
2 and proton exchange membrane 2-5-3.
Passive direct methanol fuel cell 2 in passive direct methanol fuel cell system of the present invention can also be replaced
For the battery of liquid phase feeding, mass transfer barrier layer is set in the battery of liquid phase feeding.
The present invention utilizes the reaction of mass transfer barrier layer regulating cell middle-jiao yang, function of the spleen and stomach pole plate by adding mass transfer barrier layer in battery
Methanol concentration, to adapt to cell output, to ensure the stability of passive direct methanol fuel cell system and carry
High battery performance.It is established in the application of micro-system and portable electronic product for micro direct methanol fuel battery system solid
Basis.
In the second embodiment of the present invention, a kind of passive direct methanol fuel cell system is provided, referring to Fig. 4 institutes
Show, including insulation shell 1, the passive direct methanol fuel cell 2 being arranged in insulation shell 1 and heating part 3, it is described passive
The mass transfer barrier layer 2-2 for being evenly distributed with several through-holes is equipped in the methanol chamber 2-1 of formula direct methanol fuel cell 2, for making
The methanol concentration reacted with the anode plate 2-3 of passive direct methanol fuel cell 2 adapts to cell output.
In the embodiment of the present invention, the heating part 3 uses catalysis combustion heating system, the catalysis combustion heating system
Catalytic combustor 3-1 is connected by thermostat valve with the methanol chamber 2-1 of passive direct methanol fuel cell 2, and the thermostat valve 4 is used
The break-make of catalytic combustor is flowed in control methanol intracavitary methanol, i.e., passes through thermostat valve phase between methanol chamber and catalytic combustor
Even, the break-make of thermostat valve is adjusted by solution temperature.Specifically, the catalytic combustor 3-1 of the catalysis combustion heating system is logical
Thermostat valve is crossed with the pure methanol chamber 2-1-1 of passive direct methanol fuel cell 2 to be connected.The present invention is urged using thermostat valve to control
The work for changing combustion heating system is catalyzed according to concentration of methanol solution, temperature and current density triadic relation by temperature
Burning adjusting control is realized and controls methanol flux in catalytic combustor according to temperature difference, and then regulates and controls battery temperature, to true
Cell output maximum is protected.Using methanol oxidation combustion heating, externally fed is not needed, realizes the operation of system passive type.
Shown in Figure 5 in the embodiment of the present invention, the thermostat valve 4 includes valve body 4-1, and is arranged in valve body
It is equipped with runner in shape memory alloy spring 4-2, spool 4-3 and bias spring 4-4, the valve body 4-1, the one end valve body 4-1
The inlet 4-5 communicated with runner is offered on side wall, the inlet end of valve body 4-1 extends in methanol chamber 2-1, other end position
In in the catalytic combustor 3-1 of catalysis combustion heating system.The spool 4-3 is arranged in the inlet end of valve body, the shape
Memory alloy spring 4-2 and bias spring 4-4 is located at the both ends of spool 4-3.At passive direct methanol fuel cell
When the condition of high temperature, spool is by the one end on top to inlet, thermostat valve under the action of thermostat valve is in shape memory alloy spring
Shutdown stops catalysis combustion heating.After passive direct methanol fuel cell temperature reduces to a certain extent, in biasing bullet
Thermostat valve is moved to catalytic combustor direction under the action of spring, and runner is opened, and the methanol solution of methanol intracavitary is entered by runner
Catalytic combustor heats passive direct methanol fuel cell.The stiffness factor control of adjusting bias spring can be passed through
The temperature of temperature control threshold switch processed.The thermostat valve of the present invention can also use other control valves that can realize that temperature is adjusted, to this
The present embodiment does not limit further.
Optionally, in the embodiment of the present invention, the import of the catalytic combustor of the catalysis combustion heating system is additionally provided with vapour
Liquid switch.By the way that vapour-liquid switch so is arranged around the entrance of room in catalysis.The vapour-liquid switch makes gaseous methanol
Catalysis burning can be made more abundant, liquid methanol is easier to control methanol solution break-make.Promote the performance of battery system, optimization electricity
The control condition of cell system.
Insulation shell 1 and passive direct methanol fuel cell 2 in the present embodiment and the insulation cladding in first embodiment
Body 1 and passive direct methanol fuel cell 2 are identical, and details are not described herein for the present embodiment.
The present invention carries out catalysis combustion using the methanol solution of methanol intracavitary using catalysis combustion heating system as catalyst
Heating is burnt, external heating is not needed, simplifies device, saved cost.
In the third embodiment of the present invention, a kind of passive direct methanol fuel cell system is provided, as shown in fig. 6,
The passive direct methanol fuel cell 2 being arranged in insulation shell 1 including insulation shell 1 and heating part 3, the passive type
The mass transfer barrier layer 2-2 for being evenly distributed with several through-holes is equipped in the methanol chamber 2-1 of direct methanol fuel cell 2, for make with
The methanol concentration of the anode plate 2-3 reactions of passive direct methanol fuel cell 2 adapts to cell output.
In the embodiment of the present invention, passive direct methanol fuel cell 2 and heating part 3 are integrated in insulation shell 1, heat preservation
Shell 1 is wrapped in entire battery, and heat dissipation venthole is offered on insulation shell 1.Or the insulation shell 1 uses semi-surrounding knot
Passive direct methanol fuel cell 2 and heating part 3 are surrounded wherein, the cathode side of battery are exposed by structure.The insulation cladding
Body is made of phase-change material.Using the different characteristic of the phase-change material reaction temperature of different size, using the phase of different size
Become material and is fabricated to different insulation shells.According to concentration of methanol solution, temperature and current density triadic relation, phase transformation material is determined
Material, it is extra to be absorbed using the characteristic of phase-change material when passive direct methanol fuel cell temperature is more than optimal reaction temperature
Heat, reaches temperature controlled effect, not only has the function of heat preservation, but also has the function of temperature adjusting.
Optionally, in the embodiment of the present invention, the first heat pipe 1-1, the first heat pipe 1-1 is equipped in the insulation shell 1
One end extends to catalysis combustion heating system, and in the catalytic combustor of embedded catalysis combustion heating system；The other end is by sun
Pole plate extends to the cathode plate 2-4 of passive direct methanol fuel cell.The first heat pipe 1-1 is to passive direct methanol fuel
The temperature of fuel cell and phase-change material insulation shell is balanced, and realizes the function of battery system internal temperature balance, and
First heat pipe 1-1 can be such that heat faster transmits, and improve the temperature controlled efficiency of entire cell reaction.For first
Heat pipe layout's structure the present embodiment does not limit further.
Further, shown in Figure 7 in the embodiment of the present invention, the anode of the passive direct methanol fuel cell 2
The second heat pipe 2-6 is both provided in plate 2-3 and cathode plate 2-4, the caliber T value ranges of the second heat pipe 2-6 are as follows：
0.4mm≤T≤1mm, which is micro heat pipe.The second heat pipe inside anode plate 2-3 and cathode plate 2-4 passes through insulation cladding
Body is connect with the first heat pipe in insulation shell, is passed by the heat that the second heat pipe generates passive direct methanol fuel cell
It is delivered to insulation shell, catalysis combustion heating system is then transmitted to by the first heat pipe in insulation shell, passive type is utilized
Direct methanol fuel cell reacts the waste heat of generation to improve the temperature of catalysis combustion heating system, and it is passive not only to realize
The rapid cooling of formula direct methanol fuel cell, but also the utilization again of the energy is adequately achieved, further make passive type straight
It connects methanol fuel-cell system internal temperature and reaches balance.Using micro-processing technologies such as photoetching, sputtering and corrosion in porous metals
Passive direct methanol fuel cell anode plate and cathode plate flow field structure are realized on material, by anode plate and cathode plate
Embedded ultra-thin the second Heat Pipes pole plate heat transmission optimization.
Passive direct methanol fuel cell 2 and heating part 3 and the passive type in first embodiment in the embodiment of the present invention
Direct methanol fuel cell 2 and identical with heating part 3, or with the passive direct methanol fuel cell 2 in second embodiment
Identical with heating part 3, details are not described herein for the present embodiment.
The present invention adjusts passive direct methanol fuel cell system response by insulation shell prepared by phase-change material
Temperature reaches the optimum temperature of passive type cell reaction, has saved cost, improves work efficiency.
In the fourth embodiment of the present invention, a kind of optimization method of passive direct methanol fuel cell system is provided,
Applied to the passive direct methanol fuel cell system described in first embodiment, second embodiment or 3rd embodiment,
It is shown in Figure 8, include the following steps：
Step S001:Based on the structure of the passive direct methanol fuel cell system, and combine the direct first of passive type
The multiple physical field of alcohol fuel battery establishes the Dynamic Simulation Model of passive direct methanol fuel cell system, the passive type
The Dynamic Simulation Model of direct methanol fuel cell system includes：Concentration simulation model or/and temperature simulation model；
Step S002:According to preset condition, to the Dynamic Simulation Model of the passive direct methanol fuel cell system
It is analyzed, determines each running parameter in the passive direct methanol fuel cell system.Preset condition is emulated according to concentration
Model and temperature simulation model and it is different, specific preset condition can according to those skilled in the art need be adjusted, this hair
Bright embodiment is not restricted.
In the embodiment of the present invention, the Dynamic Simulation Model of the passive direct methanol fuel cell system includes：Concentration
Simulation model；Or temperature simulation model；Or the combination of concentration simulation model and temperature simulation model.Those skilled in the art
The concrete model that the Dynamic Simulation Model of passive direct methanol fuel cell system can be selected to include according to demand.
The concentration simulation model includes one or more of following simulation model：Mass transfer barrier layer simulation model, first
Alcohol chamber simulation model, anode plate simulation model, cathode plate simulation model and membrane electrode simulation model.Wherein, the direct first of passive type
The key of concentration simulation model design is the design on mass transfer barrier layer in alcohol fuel battery system.According to hydrodynamics, methanol
Mass transfer velocity of the solution in mass transfer barrier layer is related with diffusion coefficient of the methanol solution in mass transfer barrier layer, and methanol is passing
Diffusion coefficient in matter barrier layer is again directly related with the porosity on mass transfer barrier layer, therefore the porosity on mass transfer barrier layer changes
The variation for meaning methanol concentration in cushion chamber, such as formula (1), (2) are shown.
▽·(-Deff▽ C+Cu)=R (1)
Deff=D ε1.5s1.5(2)
Wherein：DeffFor diffusion coefficient of the methanol in mass transfer barrier layer；C is methanol concentration；U is methanol in diffusion layer
Liquid phase transmission speed；R is methanol flux；D is the diffusion coefficient of methanol；S is the saturation degree of liquid；ε is the hole on mass transfer barrier layer
Gap rate.In addition the methanol concentration of methanol chamber is related with anode methanol consumption speed, and anode methanol consumption speed is faster, methanol intracavitary
Methanol concentration is lower.
The specific embodiment of the invention uses pure methanol chamber and cushion chamber with the methanol chamber of passive direct methanol fuel cell
For, cushion chamber methanol concentration depends on methanol diffusion coefficient in mass transfer barrier layer, and diffusion coefficient is related with porosity.It utilizes
This principle designs the concentration self-adapting structure of pure methanol feed flow, shown in Figure 2, by this double cavity structure and passive direct methanol
The anode of fuel cell system combines, so that it may realize that the fuel of pure methanol is accurately controlled for giving cushion chamber concentration.The present invention will
The passive direct methanol fuel cell system of the dual-chamber structure and the multiple physical field coupling of passive direct methanol fuel cell
It closes and combines, establish concentration simulation model.The concentration simulation model include mass transfer barrier layer simulation model, methanol chamber simulation model,
Anode plate simulation model, cathode plate simulation model and membrane electrode simulation model, using the porosity on mass transfer barrier layer, permeability,
The parameters such as efficient coefficient, temperature, the current density of battery of methanol solution and COMSOL, FLUENT software are to the passive type
The mass transfer barrier layer of direct methanol fuel cell system, anode plate and cathode plate, etc. structures carry out analog simulation design, obtain
Different mass transfer blocking layer porosities, mass transfer barrier layer aperture, mass transfer barrier layer hydrophobe characteristic, mass transfer barrier layer encapsulating structure etc.
Under the conditions of, the solution concentration relationship between two pure methanol chambers and cushion chamber when different working condition consumes different methanol.It is real
The cushion chamber methanol concentration in the passive direct methanol fuel cell system certain power work that M100 fuel supplies is showed
It is adaptive, the running parameter by adjusting mass transfer barrier layer makes cushion chamber concentration adapt to passive direct methanol fuel cell system
Output performance of uniting needs.Or the running parameter adjusted according to other needs that analysis result obtains.
The temperature simulation model includes one or more of following simulation model：It is catalyzed the catalysis of combustion heating system
Combustion chamber flow field simulation model, self-respiration type simulation model, thermostat valve simulation model and the guarantor for being catalyzed combustion heating system
Warm shell simulation model.In the embodiment of the present invention, temperature simulation model includes but not limited to：It is catalyzed the catalysis of combustion heating system
Combustion chamber flow field simulation model, self-respiration type simulation model, thermostat valve simulation model and the guarantor for being catalyzed combustion heating system
Warm shell simulation model.Because the key of temperature simulation model design is in passive direct methanol fuel cell system：Temperature
Control valve, the insulation shell based on different size phase-change material and the design for being catalyzed combustion heating system.
The catalytic combustor interior flow field simulation model, according to the catalytic combustor internal structure of catalysis combustion heating system
Methanol oxidation efficiency of combustion is directly affected, the present invention is modeled for the flow field structure for carrying catalyst inside catalytic combustor
Analysis, the modeling and analysis methods are identical compared with method, make the high efficiency that different interior flow field structures realizes catalysis burning.
The self-respiration type simulation model of the catalysis combustion heating system, it is burned in catalysis according to catalysis combustion heating system
The mechanism of mass transfer of oxygen and exhaust gas in journey, models self-respiration type air-exchanging structure, promotes oxygen mass transfer efficiency.
The thermostat valve simulation model, analyzes according to shape memory alloy spring, utilizes niti-shaped memorial alloy
NiTi shape is made using niti-shaped memorial alloy in the property that elasticity modulus changes with temperature linearity in certain temperature range
Niti-shaped memorial alloy spring is applied among thermostat valve by memory alloy spring.
Insulation shell simulation model absorbs heat when temperature is higher than its phase transition temperature according to phase-change material, is less than its phase alternating temperature
Exothermic property when spending realizes heat in low temperature in conjunction with the first heat pipe from catalytic combustor to cathode plate and at high temperature
Bi-directional principle of the heat from cathode plate to phase-change material, phase-change material temperature-control shell is combined by phase-change material and the first heat pipe
Layer, establishes insulation shell simulation model, realizes and accurately controlled to heat at battery pole plates, it is ensured that battery is operated in best anti-
Answer temperature.
It can be by thermostat valve simulation model, catalytic combustor interior flow field simulation model and catalysis in the embodiment of the present invention
Combustion heating system self-respiration type ventilation simulation model be coupled together, analyze catalytic combustor oxygen flow, methanol flow and
Relationship between quantity of heat production and temperature optimizes temperature configuration.Or it by insulation shell simulation model, thermostat valve simulation model, urges
The self-respiration type ventilation simulation model for changing combustion chamber flow field simulation model and catalysis combustion heating system is coupled together, excellent
Change temperature configuration.The present embodiment is not further limited this.
The temperature self-adaptation structure based on methanol oxidation combustion heat supplying is designed using principles above, it is shown in Figure 6, it will urge
Change combustion heating system and insulation shell combines with the pure methanol chamber of passive direct methanol fuel cell, realizes pure first
The catalysis combustion heat supplying and battery temperature of alcohol control.
Catalysis combustion heating system and insulation shell have been coupled with the multiple physical field of passive direct methanol fuel cell
Come, temperature simulation model is established, using softwares such as COMSOL to the battery of passive direct methanol fuel cell system, insulation cladding
Body is catalyzed combustion heating system, and thermostat valve carries out analog simulation design, will while realizing in methanol oxidation combustion heat supplying
Passive direct methanol fuel cell temperature controls the work for obtaining the phase-change material by adjusting insulation shell in a certain range
Battery temperature is set to adapt to passive direct methanol fuel cell system output performance needs as parameter.Or it is obtained according to analysis result
Go out the running parameter etc. of adjustment catalysis combustion heating system.
In the specific embodiment of the present invention, the Dynamic Simulation Model of the passive direct methanol fuel cell system
Combination including concentration simulation model and temperature simulation model builds passive direct methanol fuel cell system.Couple concentration
Simulation model and temperature simulation model are investigated battery temperature with fuel concentration to the combined influence of battery performance, are investigated emphatically
Electricity under the conditions of the variation of methanol permeability and fuel transmission-expending equilibrium in system mass transfer barrier layer in the case of different temperatures
The variation tendency of pond temperature.Present the interaction result of fuel cell system multiple physical field under actual operating conditions.
The operation principle of the present invention：When passive direct methanol fuel cell works, the methanol of pure methanol chamber is penetrating
Anode plate can be reached behind mass transfer barrier layer by diffusion and is consumed, corresponding mass transfer barrier layer specification and the direct first of passive type
Alcohol fuel battery output power can make the concentration of methanol solution of cushion chamber constant in a certain prescribed concentration, by changing mass transfer blocking
The porosity of layer changes the concentration of methanol solution in cushion chamber, realizes dense in the passive direct methanol fuel cell course of work
Adaptive, the porosity in increase mass transfer barrier layer of degree, methanol crossover quickening, current density increase, and temperature increases.In concentration
While adaptive, under the conditions of various concentration, passive direct methanol fuel cell optimal reaction temperature different problems,
The heat generated using catalysis combustion heating system is by the first heat pipe in insulation shell to passive direct methanol fuel electricity
Cathode plate, the anode plate in pond carry out quick heat supply, are increased in passive direct methanol fuel cell internal temperature, reach dense at this
Optimal reaction temperature under the conditions of degree, after reaching optimal reaction temperature, the phase-change material of insulation shell starts to absorb passive type direct
The extra heat that methanol fuel cell generates stablizes passive direct methanol fuel cell temperature in optimal reaction temperature.
Therefore, the structures such as catalysis combustion heating system of the invention, insulation shell, thermostat valve can accurately control the direct first of passive type
Temperature and concentration when alcohol fuel battery works, to adapt to and meet the needs of load performance.
Optionally, the embodiment of the present invention, the dynamic that passive direct methanol fuel cell system is established in step S001 are imitative
Before true mode, further include：
The multiple physical field of the passive direct methanol fuel cell is analyzed, methanol concentration, temperature and electricity are obtained
Correlation between current density three, to establish Dynamic Simulation Model and the analysis of passive direct methanol fuel cell system
The Dynamic Simulation Model of passive direct methanol fuel cell system provides reference frame.
The present embodiment combination micro fluid dynamics, electrochemistry, thermodynamic argument are to passive direct methanol fuel cell
Multiple physical field modeled, using finite element analysis and computational fluid dynamics related software to passive direct methanol fuel
Battery structure carry out analog simulation, analysis methanol concentration, temperature, current density to passive direct methanol fuel cell mass transfer,
The influence that diabatic process generates；Correlation between selective analysis concentration of methanol solution, temperature and current density three, and adopt
Emulation and analysis result are verified with orthogonal experimental method.It is shown in Figure 9, it is dense by analyzing the methanol solution obtained
Correlation between degree, temperature and current density three, the dynamic to establish passive direct methanol fuel cell system are imitated
True mode and the Dynamic Simulation Model of analysis passive direct methanol fuel cell system provide reference frame and provide reference frame.
Because in the passive direct methanol fuel cell course of work, participating in concentration, the temperature of methanol solution etc. of reaction
Factor is considerably complicated on performance influence, and there are substantial connections between them.It is corresponding between different output current densities
Optimum response concentration is also different, and in addition chemical reaction generates heat and can also be had an impact to battery performance.So it is straight to establish passive type
The relationship connect between the response parameters such as methanol fuel cell internal current density, concentration, temperature is the key that solve the problems, such as.This hair
It is bright to realize experimental data and models coupling, the rule contact between three can be inherently obtained, it is straight for optimization passive type
The structure for connecing methanol fuel-cell system provides foundation.
Key factor (such as concentration, temperature, current density of the embodiment of the present invention based on passive direct methanol fuel cell
Deng) analyzed, obtain the mutual balance relationship between current density, temperature and methanol concentration three and rule.Quilt of the present invention
The internal structure of dynamic formula direct methanol fuel cell system has carried out the battery system internal structure excellent by combining the relationship
Change design, the performance and job stability of passive direct methanol fuel cell system can be significantly improved.
Optionally, the embodiment of the present invention, also to the method for preparing membrane electrode of passive direct methanol fuel cell system into
Row optimization, film electrode structure shown in Figure 3, the material in substrate and microporous layers by selecting anode, cathode diffusion layer,
And optimize PTFE, Nafion polymer content being suitble in anode diffusion layer and cathode diffusion layer, improve anode and anode diffusion
The ratio of hydrophilic pores and hydrophobic hole in layer.Be not suitable for preparing relatively thin membrane electrode using conventional method, the present invention is using the method that asks
The method (CCM) of catalyst appendix film obtains the anode and cathode catalysis that relatively thin, homogeneity is good, catalyst utilization is high
Layer.The composition of anode catalyst layer and cathode catalysis layer is optimized with structure simultaneously.Optimize Nafion contents in Catalytic Layer,
Suitable and suitable pore creating material can be added in Catalytic Layer to improve the structure of anode catalyst layer and cathode catalysis layer.Intend to existing
Under the premise of having proton exchange membrane to carry out careful screening, it is (such as palladium processing) or right to be further surface-treated to proton exchange membrane
Membrane electrode carries out anti-expansion process (such as being handled with gamma-radiation), is modified membrane electrode (as led to using chemically or physically method
Cross that initiation pyrroles is aggregated in Nafion membrane and surface forms polyphosphazene polymer pyrroles) to reduce methanol crossover.Gas phase color is used respectively
The alcohol thorough rate of spectral method test film, with the conductivity of AC impedence method test film pole.With above-mentioned anode and cathode diffusion layer, catalysis
Based on layer and proton exchange membrane, the preparation process of " three in one membreane electrode " is formed.Study passive direct methanol fuel cell
The preparation process of system membrane electrode improves the performance and used life of membrane electrode.
Optionally, the embodiment of the present invention also optimizes the production method of passive direct methanol fuel cell system,
Including following method：
Passive direct methanol fuel cell system is made using MEMS technology.It is carried out using heat conduction superior metal material
Corrode into anode plate (anode current collector plate) and cathode plate (cathode collector of the perforated grill structure as direct methanol fuel cell
Plate), and the second ultra-thin heat pipe is internally embedded in cathode plate, anode plate；Using sputtering method in cathode plate and anode plate surface
Gold-plated, platinum plating (or other alloy materials), not only has preferable hydrophily, but also can reduce internal resistance, improves passive type in this way
The performance of direct methanol fuel cell system；By methanol chamber, membrane electrode, cathode collector plate, anode current collector plate, mass transfer barrier layer,
Thermostat valve is packaged into passive direct methanol fuel cell by the bonding techniques of the materials such as PDMS, finally will be catalyzed burning plus
Hot systems are integrated into insulation shell in passive direct methanol fuel cell system, are constituted based on methanol oxidation combustion heat supplying
Passive direct methanol fuel cell system.
Below by a specific example, the implementation process of the embodiment of the present invention is described in detail.
Example, shown in Figure 10, which is fired with passive miniature direct methanol
For expecting battery μ DMFC, passive type μ DMFC systems are built.It is primarily based on the passive direct methanol fuel cell system
Structure, it is shown in Figure 6, and the multiple physical field of passive direct methanol fuel cell is combined, establish passive direct methanol combustion
Expect the Dynamic Simulation Model of battery system.Including carrying out the design of mass transfer barrier layer and modeling, methanol chamber simulation model, anode plate are imitative
True mode, cathode plate simulation model and membrane electrode simulation model build concentration simulation model.Thermostat valve design and modeling are carried out,
Catalytic combustor internal process, which is designed, to be designed and builds with modeling and insulation shell with modeling, the design of self-respiration type catalytic combustor
Mould, and these types of model is combined, build temperature simulation model.
Secondly by concentration simulation model and temperature simulation models coupling, passive type μ DMFC systems are built.
Then by optimization to method for preparing membrane electrode and integration packaging optimization design, to passive type μ DMFC structures into
Row micro-nano technology.
Finally according to preset condition, passive type μ DMFC system performance analysis is carried out, determines the passive direct methanol combustion
Expect each running parameter in battery system.
Further, it before building passive type μ DMFC systems, is analyzed using the multiple physical field to passive type μ DMFC
Correlation between methanol concentration, temperature and current density three, for structure μ DMFC systems and analysis passive type μ DMFC
System performance provides reference frame.
In short, the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not intended to limit the scope of the present invention.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's
Within protection domain.
Claims (10)
1. a kind of passive direct methanol fuel cell system, which is characterized in that including insulation shell, be arranged in insulation shell
Passive direct methanol fuel cell and heating part, the methanol intracavitary of the passive direct methanol fuel cell be equipped with uniform
The mass transfer barrier layer of several through-holes is distributed with, the methanol for making to react with the anode plate of passive direct methanol fuel cell is dense
Degree adapts to cell output.
2. battery system as described in claim 1, which is characterized in that the methanol chamber of the passive direct methanol fuel cell
Including pure methanol chamber and cushion chamber, the mass transfer barrier layer is between pure methanol chamber and cushion chamber.
3. battery system as claimed in claim 1 or 2, which is characterized in that the heating part uses catalysis combustion heating system,
The methanol that the catalytic combustor of the catalysis combustion heating system passes through thermostat valve and the passive direct methanol fuel cell
Chamber is connected, and the thermostat valve is for controlling the break-make that methanol intracavitary methanol flows to catalytic combustor.
4. battery system as claimed in claim 3, which is characterized in that the catalytic combustor of the catalysis combustion heating system
Import is additionally provided with vapour-liquid switch.
5. battery system as claimed in claim 3, which is characterized in that the thermostat valve includes valve body, and is arranged in valve body
Interior shape memory alloy spring, spool and bias spring, the valve body is interior to be equipped with runner, is offered on the side wall of valve body one end
The inlet communicated with runner, the spool are arranged in the inlet end of valve body, the shape memory alloy spring and biasing bullet
Spring is located at the both sides of spool.
6. battery system as described in claim 1, which is characterized in that the insulation shell is made of phase-change material.
7. battery system as described in claim 1, which is characterized in that it is equipped with the first heat pipe in the insulation shell, described the
One heat pipe one end extends to catalysis combustion heating system, and in the catalytic combustor of embedded catalysis combustion heating system；The other end
Extend to the cathode plate of the passive direct methanol fuel cell.
8. battery system as claimed in claim 1 or 7, which is characterized in that the sun of the passive direct methanol fuel cell
The second heat pipe is both provided in pole plate and cathode plate, the caliber T value ranges of second heat pipe are as follows：0.4mm≤T≤1mm.
9. a kind of optimization method of passive direct methanol fuel cell system is applied to any electricity of claim 1 to 8
Cell system, which is characterized in that include the following steps：
Based on the structure of the passive direct methanol fuel cell system, and combine the more of passive direct methanol fuel cell
Physical field establishes the Dynamic Simulation Model of passive direct methanol fuel cell system, the passive direct methanol fuel electricity
The Dynamic Simulation Model of cell system includes：Concentration simulation model or/and temperature simulation model；
According to preset condition, the Dynamic Simulation Model of the passive direct methanol fuel cell system is analyzed, is determined
Each running parameter in the passive direct methanol fuel cell system.
10. optimization method as claimed in claim 9, which is characterized in that the concentration simulation model includes following simulation model
One or more of：Mass transfer barrier layer simulation model, methanol chamber simulation model, anode plate simulation model, cathode plate emulate mould
Type and membrane electrode simulation model；The temperature simulation model includes one or more of following simulation model：Catalysis burning adds
The catalytic combustor interior flow field simulation model of hot systems, self-respiration type simulation model, the thermostat valve for being catalyzed combustion heating system
Simulation model and insulation shell simulation model.
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