CN106207237A - There is the Proton Exchange Membrane Fuel Cells of cold-starting function - Google Patents

There is the Proton Exchange Membrane Fuel Cells of cold-starting function Download PDF

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Publication number
CN106207237A
CN106207237A CN201610749589.4A CN201610749589A CN106207237A CN 106207237 A CN106207237 A CN 106207237A CN 201610749589 A CN201610749589 A CN 201610749589A CN 106207237 A CN106207237 A CN 106207237A
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China
Prior art keywords
proton exchange
exchange membrane
fuel cells
membrane fuel
battery
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CN201610749589.4A
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Chinese (zh)
Inventor
陈蓉
杨雪
朱恂
廖强
王宏
王昊楠
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Chongqing University
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Chongqing University
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Priority to CN201610749589.4A priority Critical patent/CN106207237A/en
Publication of CN106207237A publication Critical patent/CN106207237A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1009Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/60Heating or cooling; Temperature control
    • H01M10/65Means for temperature control structurally associated with the cells
    • H01M10/659Means for temperature control structurally associated with the cells by heat storage or buffering, e.g. heat capacity or liquid-solid phase changes or transition
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04052Storage of heat in the fuel cell system
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • H01M8/04253Means for solving freezing problems
    • 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • Y02E60/10Energy storage using batteries
    • 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Fuel Cell (AREA)

Abstract

The invention discloses the Proton Exchange Membrane Fuel Cells with cold-starting function, including Proton Exchange Membrane Fuel Cells main body, described Proton Exchange Membrane Fuel Cells main body includes by anode bipolar plate, anode diffusion layer, anode catalyst layer, PEM, cathode catalysis layer, cathode diffusion layer and the cathode bipolar plate being linked in sequence of from left to right or turning left from the right side;It is characterized in that: be covered with microcapsule phase-change thermal storage material at Proton Exchange Membrane Fuel Cells body outer surface, be enclosed with photothermal deformation insulation fibre at microcapsule phase-change thermal storage material outer, outside photothermal deformation insulation fibre, be coated with optical-thermal conversion material coating;The present invention can effectively realize fuel cell low temperature and is rapidly heated and starts, and without the need for additionally consuming electric energy, effectively maintains the high energy density characteristic of battery.

Description

There is the Proton Exchange Membrane Fuel Cells of cold-starting function
Technical field
The present invention relates to fuel cell field, be specifically related to the Proton Exchange Membrane Fuel Cells with cold-starting function.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of fuel cell using hydrogen or methanol etc. as fuel, and it is single Battery is by anode bipolar plate, cathode bipolar plate, anode diffusion layer, cathode diffusion layer, anode catalyst layer, cathode catalysis layer and proton Exchange membrane forms, and fuel passes to negative electrode at anode catalyst layer oxidized generation proton and electronics, electronics by external circuit, and proton is then Pass to negative electrode by PEM, participate in reduction reaction at cathode catalysis layer.In proton conductive process, PEM begins Moistening guarantee proton to be kept passes through smoothly, and therefore water should be present in film in liquid form, and can not occur Freeze.
But owing to Proton Exchange Membrane Fuel Cells (PEMFC) sets for automobile etc. is portable often as compact power In Bei, low temperature environment to be faced, when battery does not works, internal water, it may happen that freeze, carries out cold start-up under low temperature Time, owing to internal temperature of battery is below the freezing point, causing there is no Free water, fuel cell will face and start unsuccessfully.
Microcapsule phase-change thermal storage material is to utilize Micro-Encapsulation Technique that as core, phase change heat storage material is encapsulated in glue A kind of heat-storage heat preservation material made in capsule.Phase-change material therein can utilize phase transformation material according to the change of ambient temperature Material absorbs in phase transition process or discharges amount of heat, and the hot cushioning effect formed by automatic storage heat/heat release, certain Regulation environment temperature in temperature range.If microcapsule phase-change thermal storage material to be coated in battery surface, simultaneously at electrode material Middle blending microcapsule phase-change thermal storage material, it will improve battery phase-transition heat-storage ability, thus realize the tune to internal temperature of battery Joint.
Fuel cell can produce heat in the course of the work, and additionally under illumination condition, luminous energy can also be as thermal source.As The accumulation of heat that battery produces is got up and is used when internal temperature of battery is relatively low by fruit;Simultaneously under conditions of having illumination, Convert light energy into heat energy in order to improve internal temperature of battery, then just can effectively delay or prevent under internal temperature of battery Fall, delays or prevents from freezing, thus realizing battery cold start-up.
Summary of the invention
The technical problem to be solved there are provided a kind of PEM combustion with cold-starting function Material battery.
The technical scheme is that the Proton Exchange Membrane Fuel Cells with cold-starting function, including proton exchange Membrane cell main body, described Proton Exchange Membrane Fuel Cells main body includes by the sun being linked in sequence of from left to right or turning left from the right side Pole bipolar plates, anode diffusion layer, anode catalyst layer, PEM, cathode catalysis layer, cathode diffusion layer and cathode bipolar plate; It is characterized in: be covered with microcapsule phase-change thermal storage material at Proton Exchange Membrane Fuel Cells body outer surface, in order to in battery The heat that portion's reaction produces stops or delays internal temperature of battery to decline, and improves battery cold-start condition;Scribbling microcapsule The outside batteries parcel photothermal deformation insulation fibre of phase change heat storage material, to increase cell heat transfer thermal resistance, reduces inside battery heat Amount is scattered and disappeared;Optical-thermal conversion material coating is coated, to be turned by solar energy under conditions of having illumination outside photothermal deformation insulation fibre It is changed to heat energy, improves outside batteries temperature, reduce the loss of inside battery heat.
The present invention has microcapsule phase-change thermal storage material, inside battery temperature at Proton Exchange Membrane Fuel Cells body outer surface When degree is higher than microcapsule phase-change thermal storage particle temperature, the phase change material in capsule undergoes phase transition, solid-state become liquid, absorbs electricity Heat within pond also stores;When battery temperature is less than phase transition temperature, phase change grains solidification heat release, thus can guarantee that outside When boundary's temperature is relatively low, battery temperature can the long period be maintained at above zero, it is possible to delay or stop the formation of ice.It is being coated with The battery main body outer surface having microcapsule phase-change thermal storage material wraps up photothermal deformation insulation fibre again, visible when having in external environment When light irradiates, it is possible to the effective heat energy that is converted into by luminous energy in environment, raising battery surface temperature, insulation fibre increases simultaneously Heat transfer resistance, therefore, it is possible to effectively reduce inside battery heat to Environmental diffusion.At photothermal deformation insulation fibre outer surface Cover optical-thermal conversion material coating, on the one hand can reduce inside battery heat and outwards transmit, on the other hand luminous energy can be converted For heat energy, improve battery surface temperature, reduce inside battery heat and scatter and disappear, to improve cold boot of fuel cell characteristic.Use this Several ways superposition, can improve the reliability of Proton Exchange Membrane Fuel Cells cold start-up greatly.
According to the preferred version of the Proton Exchange Membrane Fuel Cells with cold-starting function of the present invention, at anode The material of bipolar plates and cathode bipolar plate is added with microcapsule phase-change thermal storage material, to produce further with inside battery reaction Raw heat stops or delays internal temperature of battery to decline, and improves battery cold-start condition.Because, the phase change material in capsule Undergo phase transition, solid-state become liquid, absorb the heat of inside battery and store;When battery temperature is less than phase transition temperature, phase Become granule solidification heat release, thus can guarantee that when ambient temperature is relatively low, battery temperature can the long period be maintained at zero degree Above, it is possible to delay or stop the formation of ice.
According to the preferred version of the Proton Exchange Membrane Fuel Cells with cold-starting function of the present invention, microcapsule Phase change heat storage material is encapsulated in microcapsule as core for using solid-liquid phase change material.
The invention has the beneficial effects as follows: the present invention can effectively realize fuel cell internal temperature under cryogenic and keep Above freezing, delay and prevent battery from freezing to cause film irreversibility to damage, extend battery life;Further, since accumulation of heat material Material and optical-thermal conversion material all use the mode of layer, it is possible to keep the portability feature of fuel cell, without the need for additionally Consume electric energy, effectively maintain the high energy density characteristic of battery, while improving battery cold start characteristics, effectively protect electricity Pond is damaged from low temperature, has a good application prospect.
Accompanying drawing explanation
Fig. 1 is the structural representation of the Proton Exchange Membrane Fuel Cells with cold-starting function.
Detailed description of the invention
See Fig. 1, there is the Proton Exchange Membrane Fuel Cells of cold-starting function, including Proton Exchange Membrane Fuel Cells master Body, described Proton Exchange Membrane Fuel Cells main body includes anode bipolar plate 4, the sun being linked in sequence by from left to right or turning left from the right side Pole diffusion layer 6, anode catalyst layer 8, PEM 10, cathode catalysis layer 9, cathode diffusion layer 7 and cathode bipolar plate 5;Wherein, It is covered with microcapsule phase-change thermal storage material 3, at microcapsule phase-change thermal storage material 3 at Proton Exchange Membrane Fuel Cells body outer surface Outer wrap has photothermal deformation insulation fibre 2, is coated with optical-thermal conversion material coating 1 outside photothermal deformation insulation fibre 2;With Time, anode bipolar plate and cathode bipolar plate are made by the material containing microcapsule phase-change thermal storage granule.
This patent is coated in battery main body surface microcapsule phase-change thermal storage material, blends micro-glue in electrode material simultaneously Capsule phase change heat storage material, in order to store battery heat production, is released when internal temperature of battery declines and is less than the phase transition temperature of phase-change material Thermal discharge, can improve battery temperature.Meanwhile, battery surface temperature can be improved at battery surface parcel photothermal deformation insulation fibre Degree, effectively suppression inside battery heat is outwards passed.Two schemes uses simultaneously, will effectively delay internal temperature of battery in theory Reduce and the formation of ice, to improve internal temperature of battery.Thus realize there is membrane cell success cold start-up.
In a particular embodiment, the photothermal deformation insulation fibre in the present invention can use containing zirconium carbide, three oxidations two The polypropylene fibre of the optical-thermal conversion material such as aluminum, lanthanum hexaboride, research shows that this fiber has bigger near-infrared absorbing Function, the programming rate under near infrared ray irradiates is significantly greater than normal polypropylene.Photothermal deformation insulation fibre is as a kind of novel Warmth retention property functional fibre, can optionally absorb sunray and be converted into heat energy, thus being effectively improved heat insulation effect. When battery stands at low temperatures, owing to battery main body outer surface covers this photothermal deformation insulation fibre, can effectively suppress electricity Pond constant temperature reduces;Optical-thermal conversion material coating can use the photothermal deformation materials such as zirconium oxide, aluminium sesquioxide, lanthanum hexaboride Material, when sunlight irradiates, coating converts light energy into heat energy, can effectively promote battery surface temperature, and suppression internal temperature reduces.
Microcapsule phase-change thermal storage material can use the solid-liquid phase change material with suitable phase transition temperature as core, then Use microencapsulation techniques to be encapsulated in microcapsule to make.The present invention can use the materials such as caproic acid, n-tridecane, n-tetradecane Material is as core, and its phase transition temperature is respectively-7.8 DEG C ,-5.4 DEG C, 1.4 DEG C.When ambient temperature is higher than phase transition temperature, core Become liquid phase from solid phase, and by heat storage in microcapsule, when ambient temperature is less than phase transition temperature, core is become from liquid Solid-state, discharges latent heat of phase change simultaneously, promotes environment temperature.
The present invention has the effect that
(1) delay even to stop the formation of ice
The present invention wraps photothermal deformation insulation fibre at outside batteries, owing to containing oxidation in photothermal deformation insulation fibre The optical-thermal conversion materials such as zirconium, aluminium sesquioxide, lanthanum hexaboride, can effectively turn the luminous energy in environment under visible light illumination Turning to heat energy, improve battery surface temperature, insulation fibre increases heat transfer resistance simultaneously, therefore, it is possible to effectively reduce inside battery Heat is to Environmental diffusion;Battery surface brushing and in bipolar plate material add microcapsule phase-change thermal storage granule, in battery When portion's temperature is higher than the phase transition temperature of phase change heat storage material, the phase change material in capsule undergoes phase transition and is become liquid from solid-state, inhales Receive the heat of inside battery and store, when battery temperature is less than phase transition temperature, phase change grains solidification heat release.In ambient temperature relatively Time low, battery temperature can the long period be maintained at above freezing, it is possible to delay or stop the formation of ice.
(2) battery is made to start by success fast low temperature
In the case of ambient temperature is relatively low, battery can be maintained at due to heat-insulation layer and the effect of recuperation layer, internal temperature One higher temperature, like this battery cold start-up is the easiest, it is possible to the most quickly start.
It is (three) without add-on device, simple and light,
Simply change the material of electrode due to device, and wrap photothermal deformation insulation fibre in outside, outside not having Adding the machinery of complexity, the volume of battery weight does not has the biggest change, not impacts the portability of battery.Due to Simple in construction, therefore battery operation good stability, safeguard simple, low cost.
(4) battery cold start-up loss is reduced
For more existing cold boot of fuel cell devices, device of the present invention is not owing to having applied mechanical Device, the heat effectively utilizing battery to produce, decrease battery cold start-up loss.
(5) battery efficiency is improved
The energy conversion efficiency of Proton Exchange Membrane Fuel Cells, along with the raising of temperature, can improve, therefore without Opinion is that when cold start-up or when normally working, battery efficiency all can improve, when summer is sunny, and described photothermal deformation material Material can effectively convert light energy into solar energy especially, to improve battery operating temperature, makes battery efficiency be improved.
(6), the physical injury that film is caused by prevention low temperature freezing and expansion
Owing to device can effectively delay or stop the formation of ice, then the damage polymeric film knot that film causes owing to freezing Structure, cause film tympanites, rupture, the phenomenon occurrence probability bored a hole will be greatly reduced.
(7), there is general applicability
Scheme of the present invention has general applicability, not just for a certain membrane cell, for all The cold start-up of Proton Exchange Membrane Fuel Cells can play good improvement result.In addition, carry out antifreeze for needs Other battery, use above scheme, be also effective.
The present invention can successfully realize it is critical only that of cold start-up and have employed photothermal conversion, warming, phase-transition heat-storage three kinds dimension Hold the measure of internal temperature of battery.When the temperature of the surroundings is low, photothermal conversion and warming measure can effectively delay under battery temperature Reduction of speed degree, extends the time allowable that battery can stand at low temperatures, delays inside battery to freeze.When battery opens in low temperature environment Time dynamic, if internal temperature of battery is less than the phase transition temperature of microcapsule phase-change thermal storage material, then now phase-change material will be sent out Raw phase transformation, discharges heat, internal temperature of battery can be made to raise and be unlikely to freeze or tie too many ice to such an extent as to by cathode catalysis Layer covers, and it is possible to successfully realize the cold-starting of battery.

Claims (3)

1. there is a Proton Exchange Membrane Fuel Cells for cold-starting function, including Proton Exchange Membrane Fuel Cells main body, institute State anode bipolar plate, anode diffusion that Proton Exchange Membrane Fuel Cells main body includes being linked in sequence by from left to right or turning left from the right side Layer, anode catalyst layer, PEM, cathode catalysis layer, cathode diffusion layer and cathode bipolar plate;It is characterized in that: at proton Exchange film fuel battery body outer surface is covered with microcapsule phase-change thermal storage material, wraps up at microcapsule phase-change thermal storage material outer There is photothermal deformation insulation fibre, outside photothermal deformation insulation fibre, be coated with optical-thermal conversion material coating.
The Proton Exchange Membrane Fuel Cells with cold-starting function the most according to claim 1, it is characterised in that: and And, the material of anode bipolar plate and cathode bipolar plate is added with microcapsule phase-change thermal storage material.
The Proton Exchange Membrane Fuel Cells with cold-starting function the most according to claim 1 and 2, it is characterised in that: Microcapsule phase-change thermal storage material is encapsulated in microcapsule as core for using solid-liquid phase change material.
CN201610749589.4A 2016-08-29 2016-08-29 There is the Proton Exchange Membrane Fuel Cells of cold-starting function Pending CN106207237A (en)

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Cited By (10)

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Publication number Priority date Publication date Assignee Title
CN106784922A (en) * 2017-02-15 2017-05-31 天津大学 Using the logical direct current electrical heating Proton Exchange Membrane Fuel Cells cold-starting device of graphite cake
CN107123823A (en) * 2017-04-26 2017-09-01 乐山伟力得能源有限公司 A kind of thermal management algorithm applied to flow battery
CN108199118A (en) * 2018-02-10 2018-06-22 宿州市艾尔新能源有限公司 A kind of metal-air battery using phase-change temperature control
CN108257795A (en) * 2018-01-10 2018-07-06 北京石墨烯研究院 A kind of method for improving ultracapacitor capacitance
CN108470639A (en) * 2018-04-04 2018-08-31 中国科学院兰州化学物理研究所 The ultracapacitor of low-temperature working
CN108630460A (en) * 2018-04-04 2018-10-09 中国科学院兰州化学物理研究所 Color function type ultracapacitor
CN108736104A (en) * 2018-08-02 2018-11-02 广东电网有限责任公司 A kind of high temperature resistant battery
CN111945300A (en) * 2020-08-17 2020-11-17 中国科学院合肥物质科学研究院 Composite material with photo-thermal conversion and storage and discharge functions, preparation method and application
CN114243165A (en) * 2021-12-14 2022-03-25 重庆大学 Lithium ion battery thermal management system
CN114373964A (en) * 2022-02-17 2022-04-19 山东大学 Fuel cell cold start and heat preservation system and method utilizing solar energy

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Publication number Priority date Publication date Assignee Title
CN106784922B (en) * 2017-02-15 2023-09-22 天津大学 Cold starting device for heating proton exchange membrane fuel cell by using graphite plate to supply direct current
CN106784922A (en) * 2017-02-15 2017-05-31 天津大学 Using the logical direct current electrical heating Proton Exchange Membrane Fuel Cells cold-starting device of graphite cake
CN107123823A (en) * 2017-04-26 2017-09-01 乐山伟力得能源有限公司 A kind of thermal management algorithm applied to flow battery
CN108257795A (en) * 2018-01-10 2018-07-06 北京石墨烯研究院 A kind of method for improving ultracapacitor capacitance
CN108199118A (en) * 2018-02-10 2018-06-22 宿州市艾尔新能源有限公司 A kind of metal-air battery using phase-change temperature control
CN108199118B (en) * 2018-02-10 2023-10-10 宿州市艾尔新能源有限公司 Metal-air battery adopting phase change temperature control
CN108470639A (en) * 2018-04-04 2018-08-31 中国科学院兰州化学物理研究所 The ultracapacitor of low-temperature working
CN108630460A (en) * 2018-04-04 2018-10-09 中国科学院兰州化学物理研究所 Color function type ultracapacitor
CN108736104A (en) * 2018-08-02 2018-11-02 广东电网有限责任公司 A kind of high temperature resistant battery
CN111945300A (en) * 2020-08-17 2020-11-17 中国科学院合肥物质科学研究院 Composite material with photo-thermal conversion and storage and discharge functions, preparation method and application
CN114243165A (en) * 2021-12-14 2022-03-25 重庆大学 Lithium ion battery thermal management system
CN114243165B (en) * 2021-12-14 2023-10-31 重庆大学 Lithium ion battery thermal management system
CN114373964A (en) * 2022-02-17 2022-04-19 山东大学 Fuel cell cold start and heat preservation system and method utilizing solar energy
CN114373964B (en) * 2022-02-17 2023-08-11 山东大学 Fuel cell cold start and heat preservation system and method utilizing solar energy

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Application publication date: 20161207

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