WO2013155700A1 - 防止自身过热的储能系统、防止储能系统过热的方法、和在储能系统上形成散热涂层的方法 - Google Patents

防止自身过热的储能系统、防止储能系统过热的方法、和在储能系统上形成散热涂层的方法 Download PDF

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Publication number
WO2013155700A1
WO2013155700A1 PCT/CN2012/074434 CN2012074434W WO2013155700A1 WO 2013155700 A1 WO2013155700 A1 WO 2013155700A1 CN 2012074434 W CN2012074434 W CN 2012074434W WO 2013155700 A1 WO2013155700 A1 WO 2013155700A1
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WIPO (PCT)
Prior art keywords
energy storage
coating
storage system
high emissivity
heat
Prior art date
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PCT/CN2012/074434
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English (en)
French (fr)
Inventor
金虹
布瑞姆尔•乔治•H.
尼斯普•麦克•T.
任冬雪
Original Assignee
北京低碳清洁能源研究所
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Application filed by 北京低碳清洁能源研究所 filed Critical 北京低碳清洁能源研究所
Priority to US14/395,378 priority Critical patent/US9647303B2/en
Priority to PCT/CN2012/074434 priority patent/WO2013155700A1/zh
Priority to CN201210382015.XA priority patent/CN103378382B/zh
Publication of WO2013155700A1 publication Critical patent/WO2013155700A1/zh

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6551—Surfaces specially adapted for heat dissipation or radiation, e.g. fins or coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/613—Cooling or keeping cold
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/655—Solid structures for heat exchange or heat conduction
    • H01M10/6553—Terminals or leads
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
    • H01M50/1245—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure characterised by the external coating on the casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/209—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for prismatic or rectangular cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
    • H01M50/24—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries from their environment, e.g. from corrosion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/251—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders specially adapted for stationary devices, e.g. power plant buffering or backup power supplies
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/502—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing
    • H01M50/507—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing comprising an arrangement of two or more busbars within a container structure, e.g. busbar modules
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/502—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing
    • H01M50/521—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing characterised by the material
    • H01M50/522—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/502—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing
    • H01M50/521—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing characterised by the material
    • H01M50/526—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing characterised by the material having a layered structure
    • Y—GENERAL 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
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • An energy storage system that prevents self-heating, a method of preventing overheating of the energy storage system
  • the invention relates to an energy storage system for preventing self-heating, in particular to a battery and a system thereof, in particular to a valve-regulated lead-acid battery and a system thereof, and to a method for preventing overheating of an energy storage system. And a method of forming at least one layer of high emissivity heat dissipating coating on an energy storage system or at least a portion of an outer surface of an energy storage system component.
  • a battery and its system as one of the energy storage systems, are devices that store electrical energy to obtain the required energy when needed.
  • a battery typically includes two electrodes, an anode and a cathode, disposed in an electrolyte. As is known in the art, the electrical equipment being operated is typically connected across its cathode and anode as needed to obtain electrical energy from the battery.
  • Lead-acid batteries as one of the batteries, have been in existence for 150 years since they were discovered in 1859. During this period, lead-acid batteries were widely used in power, communications, railway, petroleum, aviation, water, coal, geology, medical, rail transit, defense and other fields.
  • a lead-acid battery is a device that converts electrical energy into chemical energy and, when needed, converts chemical energy into electrical energy to supply electrical equipment. Its positive active material is lead dioxide (Pb0 2 ), the negative active material is spongy metal lead (Pb), and the electrolyte is sulfuric acid (H 2 S0 4 ).
  • the charging and discharging processes are carried out by electrochemical reactions. As shown in the following reaction equation, lead (negative electrode) and lead oxide (positive electrode) react with sulfuric acid to form lead sulfate during discharge of a lead-acid battery.
  • the charging process is the reverse reaction of the discharge process.
  • Lead-acid battery has a market share of more than 50% due to its low cost and mature technology, which shows its strong vitality.
  • Traditional lead-acid batteries are mostly used in small-scale low-power applications such as auxiliary devices or backup power supplies. Therefore, overheat faults and heat dissipation problems are not prominent, and there is no specific solution.
  • Lead-acid batteries are also starting Used for uninterrupted power supply units. This also puts new demands on lead-acid batteries and other types of batteries.
  • the solution often adopted is to enlarge the volume of the battery.
  • the battery has a larger capacity, and the relative discharge depth becomes smaller during discharge, thereby increasing the life of the battery.
  • this method greatly increases production costs and operating costs.
  • the existing lead-acid batteries are mainly divided into overflow type and valve control type.
  • the valve-regulated lead-acid battery is more difficult to dissipate heat, because: in the overflow type lead-acid battery cell, excess electrolyte fills the three-dimensional space of the battery cell except the electrode, thereby To improve the thermal contact between the internal components of the battery cells, and during charging, the generated gases carry heat away from the battery cells by losing moisture to form an acid mist.
  • a separator such as an adsorbed glass fiber cloth, there is not a large amount of free acid present, acid, diaphragm, and plate.
  • the overheating of VRLA batteries comes mainly from two parts: one is chemical exotherm.
  • the chemical exotherm is very intense, and only the oxygen composite reaction reaches 68.32kcal/mol during charging. Therefore, during the repeated charge and discharge process, the exothermic rate is extremely high, and it is easy to reach above 80 °C, so that it is overheated; It is derived from ohmic heat (resistance heat generated by the grid, bus bar, diaphragm, end pole, etc. of the battery).
  • the heat is generated from the inside, and the outer casing of the battery cell is generally made of a polymer material, the heat can be dissipated from the battery component of the metal plate such as the grid plate, the bus bar, and the end pole, but the heat dissipation area is very large. Limited, so the heat inside the battery unit is not easily dissipated.
  • No. 7,518,811 discloses a traction battery comprising a plastic cover with venting holes for covering electrical connection strips. The fan forces air to flow through the battery's electrical connection strips, which is used to lower the operating temperature of the battery.
  • U.S. Patent 3,834,945 discloses the use of water to cool the electrical connection bars between the end posts of the traction battery and the battery cells. Whether it is air-cooled or water-cooled, the heat transfer effect of the electrical connecting strip is limited, so the heat transfer effect is not very obvious.
  • the structural design with the function of cooling the battery such as the addition of a water cooling system or a fan, tends to make the overall structure of the battery more complicated, bulky and cumbersome, and complicates the maintenance and installation process.
  • CN200952916Y discloses an improved structure of a heat dissipating device for improving heat dissipation efficiency of mechanical heat generated during operation of a mechanical device, wherein a nano carbon layer is physically attached outside the machine heat sink to increase overall heat dissipation.
  • the area and the rapid heat dissipation characteristics of the nano-carbon layer improve the heat dissipation effect of the heat sink.
  • this document does not specifically disclose the effective composition of the nanocarbon layer, and does not teach or suggest that the nanocarbon layer is used in other fields.
  • the present invention is directed to making one or more improvements to the above-discussed deficiencies in the prior art.
  • SUMMARY OF THE INVENTION The present invention aims to provide an energy storage system for preventing self-heating and a method for preventing overheating of an energy storage system, so that the energy storage system has a good heat dissipation effect, and the operating temperature is too high under high power charging and discharging conditions. Therefore, the service life thereof is prolonged, and the energy storage system of the present invention does not have the problem of complicated installation.
  • Another object of the present invention is to provide a method of forming at least one layer of high emissivity heat dissipating coating on an energy storage system or at least a portion of an outer surface that forms an assembly of the energy storage system.
  • the above objects are achieved by an energy storage system having the following features:
  • the energy storage system includes a heat dissipating outer surface, wherein at least a portion of the outer surface is coated with at least one layer of high emissivity heat dissipating coating.
  • the outer surface comprises an energy storage system itself, an energy storage unit constituting the energy storage system, an electrical connection (strip) between the energy storage units, an end pole of the energy storage unit, or an exposed surface of the support.
  • Applying a high emissivity heat-dissipating coating on an exposed heat-dissipating surface such as an end post and/or an outer surface of the electrical connector while dissipating heat from the heat dissipating surface by radiation, convection, and/or heat conduction
  • the transfer and diffusion of the surrounding environment which in turn causes the temperature of the exposed heat-dissipating surface of the outer surface such as the end pole and/or the electrical connector to rapidly decrease, in particular, since the terminal post and/or the electrical connector have a self-storing unit interior
  • the effect of heat conduction to the outside, the rapid decrease of the temperature of the outer surface of the terminal post and/or the electrical connector can further reduce the temperature inside the energy storage unit, and thus, in this way, the operating temperature of the energy storage system is
  • the high emissivity heat dissipation coating contains nanoparticles or the like.
  • the nanoparticles or the like are carbon nanotubes, nanorods, nanospheres, nanoparticles, and the like.
  • the nanoparticles or analogs have a particle size of less than 100 nanometers.
  • the high emissivity heat dissipating coating has a black body emissivity of greater than 0.8 at 300 K and a thermal conductivity of greater than 150 W/m ⁇ ⁇ in order to facilitate heat dissipation of the energy storage system.
  • the high emissivity heat dissipation coating comprises various oxides such as SiO 2 , ZrO 2 , CrO 2 , A1 2 0 3 , and/or various carbides such as ZrC, SiC, and/or various nitrides. , for example, Si 3 N 4 .
  • the coating composition, thickness, or curing temperature and time of each layer may be the same or different.
  • each coating thickness is less than or equal to 200-300 microns.
  • a high emissivity heat-dissipating coating doped with nanoparticles or the like, such as carbon nanotubes on the exposed heat-dissipating surface of the energy storage system, one or more layers of high emissivity heat-dissipating coating may be formed on the same surface.
  • the layers therefore, the coating can be applied one or more times, and each coating can be cured at a temperature equal to or higher than room temperature, for example, 50 °C.
  • the number of layers of the high emissivity heat dissipation coating layer may be 2, 3, or 4.
  • a high-radiation heat-dissipating coating is applied in two steps to four steps on the exposed heat-dissipating surface of the energy storage system, for example, on the exposed heat-dissipating surface of the terminal pole and/or the electrical connector (strip).
  • the high emissivity heat dissipation coating the heat dissipation effect and heat dissipation speed of the heat dissipation surface are significantly improved.
  • the energy storage system can be a battery and its system, especially a valve regulated lead acid battery and its system.
  • the present invention provides a method of preventing overheating of an energy storage system, the energy storage system including an outer surface that dissipates heat, wherein at least a portion of high emissivity heat dissipation is formed or coated on at least a portion of the outer surface coating.
  • the present invention provides a method of coating or forming at least one layer of high emissivity heat dissipating coating on an energy storage system or at least a portion of an outer surface of an energy storage system component, comprising the steps of: (1) mixing The effective component of the coating or its precursor is stirred until a uniform coating mixture is formed; (2) applying the above uniform coating mixture to the at least part of the outer surface to form a homogeneous coating; (3) at or equal to Curing the coating at a curing temperature above room temperature until fully cured; (4) Optionally, repeating steps (1), (2), and (3) above in sequence to form a plurality of at least portions of the outer surface Layer high emissivity heat dissipation coating.
  • a plurality of layers of high emissivity, heat dissipating coating such as 2-4 layers, are coated or formed on at least a portion of the outer surface as described above.
  • the coatings have a curing temperature of from 40 °C to 100 °C, for example 50 °C. Selecting the curing temperature within this range may be advantageous in forming a coating having a large number of pores and microcracks, which further enhances the heat radiation effect.
  • a high emissivity heat-dissipating coating such as a heat-dissipating coating doped with carbon nanotubes
  • the exposed heat-dissipating surface of the energy storage system such as the end poles and/or the outer surface of the electrical connecting strip
  • the system can expose a heat dissipation surface with high emissivity characteristics, which enhances heat exchange between the heat dissipating surface and the surrounding environment, thereby facilitating rapid cooling of the heat dissipating surface, thereby reducing the operating temperature of the energy storage system and extending The service life of the energy storage system.
  • FIG 1 is an overall schematic view of a conventional energy storage system, such as a battery system;
  • Figure 2 is a schematic diagram of an electrical energy storage strip (piece) of an existing energy storage system, such as a battery system, for connecting a battery cell (storage unit) end pole.
  • Figures 3a-3c are electrical connections of a high emissivity heat-dissipating coating coated on one side with a layer of high emissivity heat-dissipating coating at room temperature, 50 ° C, and 100 ° C, respectively, and conventional electrical connections that are not coated with a high emissivity heat-dissipating coating. a comparison chart of the heat dissipation capability of the strip;
  • Figure 4 is a graph comparing the heat dissipation capability of an electrical connection strip coated with a high emissivity heat-dissipating coating cured at room temperature on both sides and a conventional electrical connection strip not coated with a high emissivity heat-dissipating coating;
  • Figure 5a-5b is a comparison of the heat dissipation capability of an electrical connection strip coated with two layers and three layers of a high emissivity heat-dissipating coating that is cured at room temperature and a conventional electrical connection strip that is not coated with a high emissivity heat-dissipating coating.
  • Figure 5c is a graph comparing the heat dissipation capability of an electrical connection strip coated with two layers of a high emissivity heat-dissipating coating cured at 50 ° C on both sides and a conventional electrical connection strip not coated with a high emissivity heat-dissipating coating;
  • Figure 5d is a comparison of the heat dissipation capability of an electrical connection strip coated with three layers of high emissivity heat-dissipating coating cured at 50 ° C on both sides and a conventional electrical connection strip not coated with a high emissivity heat-dissipating coating.
  • Figure 6a is a battery connected to an electrical connection strip coated with two layers of high emissivity heat-dissipating coating cured at 50 ° C on both sides and with a high emissivity heat-dissipating coating on either side.
  • Figure 6b shows a battery connected to an electrical connection strip coated with two layers of high emissivity heat-dissipating coating cured at 50 ° C on both sides and with a high emissivity heat-dissipating coating on either side.
  • FIG 1 is a schematic illustration of one embodiment of a prior art energy storage system (generally referred to as an electrical energy storage system).
  • the energy storage system can be a battery and its system, a capacitor and its system, or other chemical or physical energy storage device.
  • the battery system will be described as an example below.
  • Battery system 1 includes a plurality of battery cells (storage unit)
  • Each battery cell 10 can have one or more battery cells (energy storage cells).
  • the plurality of battery cells 10 can be arranged in any array.
  • Each of the battery cells 10 has two terminal posts 101 (positive terminal poles) and 102 (negative terminal poles) which are led out from the inside.
  • the electrical connection between the individual battery cells 10 is achieved by means of electrical connection strips (pieces) 13.
  • Electrical connection strip 13 - end and positive pole of a battery unit 10 The terminal post 101 is connected, and the other end is connected to the negative terminal post 102 of the other battery unit 10.
  • the electrical connection strips 13 are made of a conductive material for conducting current between the battery cells 10.
  • the battery system 1 further includes an end pole (pole) for electrically connecting to an external circuit, that is, a positive pole and a cathode pole.
  • the conventional electrical connecting strip 13 is a flat plate having a smooth surface, and has connecting holes 131, 132 for connecting the end posts at both ends of the electrical connecting strip 13.
  • the electrical connecting strip 13 is made of copper and has a size of 85 mm (length) X 30 mm (width) X 2 mm (thickness). A large amount of heat is generated during charging and discharging of the battery and its system. Due to its structural characteristics, the end poles, the electrical connecting strips, the metal grid and the like constitute a heat conductor for conducting and diffusing heat from the internal space of the battery unit 10.
  • one or more layers of high emissivity heat dissipating coating are formed or coated on the exposed heat dissipating surface of the terminal post and/or the electrical connecting strip, the heat dissipating coating being formed by a high emissivity heat dissipating coating.
  • the high emissivity heat dissipating coating includes various oxides such as SiO 2 , ZrO 2 , CrO 2 , Al 2 2 3 3 , and/or various carbides such as ZrC, SiC, and/or various nitrides, for example Si 3 N 4 .
  • the high emissivity heat dissipation coating has been reported to be widely used in mechanical equipment such as an aerospace spacecraft, a boiler, an oven, and the like.
  • high emissivity heat-dissipating coating refers to a coating having a higher emissivity than the surface to be coated in a wide wavelength range (e.g., 1-20 ⁇ m).
  • the high emissivity heat dissipating coating comprises or is doped with nanoparticles or the like.
  • a coating containing nanoparticles or the like is called a nano-coating, and the coating formed by it is called a nano-coating. More preferably, the nanoparticles or the like have a particle size of less than 100 nanometers.
  • examples of the nanoparticles or the like are carbon nanotubes, nanorods, nanospheres, or nanoparticles, and the like.
  • a coating containing carbon nanotubes is called a carbon nanotube coating, and the coating formed is called a carbon nanotube coating.
  • the emissivity of the coating or coating depends primarily on its composition and is very sensitive to the structure of the coating itself and the surface state of the surface to which it is attached. Factors affecting the emissivity of the coating include coating doping, coating surface roughness and/or surface texture, coating thickness, and the like. Carbon nanotubes have carbon-carbon chemical bonds, high emissivity, good thermal conductivity, high strength, and large specific surface area. Doping carbon nanotubes into coatings not only improves the tensile strength and fracture toughness of the coating, but also provides a large number of new interfaces between the carbon nanotubes and the coating matrix, resulting in more electromagnetic reflections inside the coating. Therefore, it is possible to absorb more heat in the form of electromagnetic waves.
  • the high emissivity heat dissipating coating or coating has a black body emissivity greater than 0.8 at 300 K and a thermal conductivity greater than 150 W/m ⁇ K.
  • the formation or application of a high emissivity heat dissipating coating on the exposed heat dissipating surface of the outer surface of, for example, the electrical and/or end posts accelerates the diffusion of heat from the coated surface to the surrounding environment. The reason is that the high emissivity of the coating itself will help to increase the emissivity of the surface on which the coating is located.
  • coating the coating containing nanoparticles results in, for example, electrical connecting strips and/or end plates.
  • the outer surface of the column becomes rough, thereby increasing the exposed heat dissipation surface of the entire energy storage system, thereby increasing the reflection of electromagnetic waves. This causes heat to rapidly radiate and diffuse energy from, for example, the outer surface of the electrical connecting strip and/or the end post to the surrounding environment, thereby reducing the temperature of the exposed surface of the end post.
  • the terminal post constitutes a heat diffusion channel from the inside of the battery unit
  • the temperature difference between the portion of the terminal pole located inside the battery unit and the exposed portion is increased, thereby causing heat to quickly pass from the inside of the battery unit to the electrical connection strip and / /
  • the exposed surface of the end pole conducts and spreads, thus, as a whole, can quickly transfer heat from the inside of the battery unit to the external environment, thereby reducing the operating temperature of the battery and its system, and extending the service life of the battery.
  • each of the above high emissivity heat dissipating coating layers is preferably less than or equal to 200 to 300 ⁇ m.
  • a plurality of layers are formed or coated on the exposed surfaces of the electrical and/or end posts by a multi-step, such as a two-step to four-step coating process.
  • a high emissivity heat dissipating coating wherein the coating process of each layer of paint comprises the following steps: (1) mixing an effective component of the high emissivity heat dissipating paint or a precursor thereof, and stirring to form a uniform coating mixture; Applying a uniform coating mixture to the outer surface to form a homogeneous coating; (3) curing the above homogeneous coating at a curing temperature of room temperature or above until completely cured, for example, baking for 4-24 hours .
  • a solvent and/or a binder for improving the adhesion of the coating may also be contained.
  • the curing temperature and curing time of each layer may be the same or different.
  • rapid temperature rise can enclose the formed gas inside the coating, which may form pores, micro-interfaces, and/or micro-cracks, which will facilitate the formation of more A porous layer that reflects the interface of electromagnetic waves, and therefore, can obtain better absorption and radiation characteristics.
  • the curing temperature of each layer of the high emissivity heat dissipation coating layer is from 40 ° C to 100 ° C, for example, 50 ° C.
  • the overlapping arrangement between the different coatings introduces an additional interface between the coatings, which in turn may generate more microcracks which are favorable for reflection, Stomata, and / or micro interface layer, this will be more It helps to increase the radiance of the entire coating and accelerate the outward diffusion and transfer of heat from the coated surface.
  • the coating composition, thickness, curing temperature and curing time of each coating layer may be the same or different.
  • the following is an example of a flat electrical connection strip (piece) for the heat dissipation capability of a conventional electrical connection strip and an electrical connection strip coated with a carbon nanotube coating (a high emissivity heat dissipation coating containing carbon nanotubes) or The heat storage capacity is compared.
  • the carbon nanotube coating is a commercially available Zhisheng coating ZS-411 type.
  • the surface temperatures of the above two electrical connecting strips were measured and compared for different coatings and different coating conditions over a time period of approximately 1500 seconds. It has been found that the surface temperature of the electrical connecting strip of the present invention is significantly lower than the surface temperature of the conventional electrical connecting strip, which indicates that the heat dissipation capability of the electrical connecting strip of the present invention is much greater than that of the conventional electrical connecting strip.
  • the temperature (i.e., curing temperature) of the cured coating layer can be selected within a temperature range of room temperature to 100 °C.
  • the electrical connection bars coated with coatings cured at different temperatures are compared to the heat dissipation capabilities of conventional electrical connection strips that are not coated with a high emissivity heat dissipation coating.
  • an electrical connection strip coated with a layer of carbon nanotube coating cured at room temperature, 50 ° C, and 100 ° C was tested and found to have a curing temperature of room temperature. (Approximately 20 ° C), the maximum surface temperature difference between the electrical connecting strip of the present invention and the conventional electrical connecting strip is 19.
  • the curing temperature is about 50 °C. Theoretically, the larger the area of the coating formed or coated on the exposed heat dissipating surface, the faster the heat dissipation rate.
  • Figure 3a is a comparison of the surface temperature of a conventional carbon strip coated with a layer of carbon nanotube coating cured at room temperature with a conventional electrical connecting strip.
  • the maximum surface temperature difference between the electrical connecting strip of the present invention and the conventional electrical connecting strip is 19. 4 ° C.
  • Figure 4 is a comparison of the surface temperature of the electrical connecting strip coated with a layer of carbon nanotube coating cured at room temperature on both sides and the conventional electrical connecting strip.
  • the maximum surface temperature difference between the electrical connecting strip of the present invention and the conventional electrical connecting strip is 53. . 8 ° C. Therefore, preferably, the nanoparticle is formed or coated on both sides of an electrical energy storage strip of an energy storage system, such as a battery and its system. Or a similar coating of high emissivity heat-dissipating coating.
  • FIG. 5a is a comparison of the heat dissipation capability of an electrical connection strip coated with two layers of carbon nanotube coating cured at room temperature on one side and an electrical connection strip conventionally not coated with a high emissivity heat dissipation coating, the electrical connection strip of the present invention
  • the maximum surface temperature difference of the conventional electrical connecting strip is 26.9 ° C ;
  • 5b is an electrical connecting strip coated with three layers of carbon nanotube coating cured at room temperature on one side and a conventional high-radiation heat-dissipating coating without coating. 5 ° C ⁇
  • the maximum surface temperature difference between the electrical connection strip of the present invention and the conventional electrical connecting strip is 37. 5 ° C.
  • the electrical connection strips coated with two layers of carbon nanotube coating on both sides are the largest with the conventional electrical connection strips not coated with a high emissivity heat dissipation coating.
  • the surface temperature difference is 51. 9 ° C; likewise, as shown in Figure 5d, the electrical connection strips coated on both sides with three layers of carbon nanotube coating and the conventional electrical connection strips not coated with a high emissivity heat dissipation coating
  • the maximum surface temperature difference is 46. 4 ° C. Therefore, preferably, two layers of carbon nanotube coating are applied on both sides of the electrical connection strip at a curing temperature of 50 °C.
  • valve-regulated lead connected to a galvanic lead-acid battery of the present invention coated with a carbon nanotube coating and an electrical connection strip to which an uncoated carbon nanotube coating is attached
  • the heat-dissipating capacity of the acid battery is compared.
  • the valve-regulated lead-acid batteries used are all Leoch DJ100.
  • the electrical connecting strip of the present invention connected to a VRLA battery is coated on both sides with two layers of carbon nanotube coating cured at 50 °C.
  • thermocouples In order to simulate the exothermic situation of different batteries after absorbing the equivalent heat, first, the battery is heated in a heating furnace at a certain temperature until a steady state is reached, and then the battery is naturally cooled, during which different parts of the battery are made by thermocouples. Temperature measurement. It has been found experimentally that the temperature of the battery of the invention (typically the temperature of the positive and negative poles) is reduced at a faster rate than that of a conventional battery, producing a temperature of 3-4 ° C in 7 minutes. The drop is 16% faster than the conventional battery, as shown in Figures 6a and 6b, wherein Figure 6a is a comparison of the temperature changes of the negative pole of the battery, and Figure 6b is a comparison of the temperature changes of the positive pole of the battery.
  • Figure 6a is a comparison of the temperature changes of the negative pole of the battery
  • Figure 6b is a comparison of the temperature changes of the positive pole of the battery.
  • the surface capable of coating the high emissivity heat dissipation coating is not limited to the outer surface of the terminal post and/or the electrical connecting strip, but may also include the energy storage.
  • said forming or coating at least a portion of the high emissivity heat dissipating coating on at least a portion of the exposed heat dissipating surface Layered The method has better applicability and can more effectively reduce the operating temperature of the energy storage system.
  • the method of forming or coating at least a portion of the high emissivity heat dissipating coating on at least a portion of the exposed heat dissipating surface may be used alone or in combination with other prior art techniques for enhancing heat dissipation, such as adding a fan to enhance convective heat dissipation of the exposed heat dissipating surface. .
  • the electrical connection bar or the end pole itself has a very small resistance.
  • heat dissipating coating such as a carbon nanotube coating
  • the change in electrical resistance of the electrical and/or end posts can be negligible.

Abstract

本发明公开了一种防止自身过热的储能系统，包括散热的外表面，其中，所述外表面的至少一部分上涂覆有至少一层高辐射率散热涂层。本发明还公开了一种防止储能系统过热的方法、以及一种在储能系统或构成储能系统组件的至少部分外表面上形成至少一层高辐射率散热涂层的方法。

Description

防止自身过热的储能系统、 防止储能系统过热的方法、
和在储能系^ ±形成散热涂层的^ 技术领域
本发明涉及一种防止自身过热的储能系统，特别是，一种蓄电池及其系统， 尤其特别是， 一种阀控式铅酸蓄电池及其系统， 本发明还涉及一种防止储能系 统过热的方法和一种在储能系统或构成储能系统组件的至少部分外表面上形成 至少一层高辐射率散热涂层的方法。
背景技术
蓄电池及其系统， 作为储能系统中的一种， 是储存电能以在需要时得到所 需能量的装置。蓄电池典型地包括安置在电解质中的两个电极，即阳极和阴极。 如在相关技术中已知的， 在需要时， 通常将被操作的电气设备跨接在其阴极和 阳极两端， 以从蓄电池中得到电能。
蓄电池具有很多种类。 铅酸蓄电池， 作为蓄电池中的一种， 自 1859年被发 明至今已有 150年的历史。 在这期间， 铅酸蓄电池广泛应用于电力、 通信、 铁 路、 石油、 航空、 水利、 煤炭、 地质、 医疗、 轨道交通、 国防等领域。
铅酸蓄电池是将电能转换为化学能储存起来， 需要时又将化学能转变为电 能供给用电设备的装置。 它的正极活性物质是二氧化铅（Pb02 ) ， 负极活性物质 是海绵状金属铅 （Pb ) ， 电解液是硫酸液 （H2S04 ) 。 其充电和放电过程是通过 电化学反应实现的。如下列反应方程式所示，在铅酸蓄电池的放电过程中铅（负 极）和氧化铅（正极）与硫酸反应生成硫酸铅。充电过程是放电过程的逆反应。
正极反应： Pb02+4H++S04 2— +2e— PbS04+2H20
负极反应： Pb+S04 2— PbS04+2e"
总反应： Pb02+Pb+2H2S04 2PbS04+2H20 铅酸蓄电池由于成本较低，技术成熟，目前仍然具有 50%以上的市场占有率， 这显示出其强大的生命力。 传统铅酸蓄电池大多是应用在辅助装置或备用电源 等小规模低功率的应用场合， 故过热故障和散热问题并不突出， 也没有专门的 解决方案。 但随着智能电网概念的提出， 以及可再生能源发电 （风能、 太阳能 等） 装机量日益增长， 建设大规模储能装置势在必行。 目前铅酸蓄电池也开始 用于不间断的电源装置。 这也给铅酸蓄电池以及其它种类电池提出了新要求。 例如， 当储能系统应用在大规模储能场合时， 这种应用往往是高功率、 多周期 的， 所以过热问题十分突出， 这将直接影响其使用寿命。 在大功率的应用中， 铅酸蓄电池及其系统的过热问题会使得电池及其系统烧结、 老化、 甚至坏损。 因此， 如果将铅酸蓄电池应用于大型储能系统中， 热控制或热管理水平将直接 影响铅酸蓄电池及其系统的寿命。
传统工业中，为了克服该问题，常常采用的解决方式是将电池的体积放大。 如此一来， 电池具有更大的容量， 放电时相对放电深度就会变小， 从而提高了 电池的寿命。 但是这种方法大大增加了生产成本与运营成本。 现有铅酸蓄电池主要分为溢流式和阀控式。 相比于溢流式铅酸蓄电池， 阀 控式铅酸蓄电池更难散热， 原因在于： 在溢流式铅酸蓄电池单体中过量电解质 填充电池单体中除电极以外的三维空间中， 从而起到改进电池单体内部构件之 间热接触的作用， 并且在充电过程中， 所产生的气体通过丢失水分以形成酸雾 的形式而将热量从电池单体内带走。 相比之下， 在阀控式铅酸蓄电池单体中， 由于酸液是由隔膜、 如吸附式玻璃纤维布吸收饱和的， 因此并没有大量游离的 酸液存在， 酸液、 隔膜、 极板与塑料外壳壁之间的接触有限， 从而限制了热量 从电池单体内部传递出去， 并且缺少自电池内部到电池外部的气体释放通道， 因而充放电过程所产生的热量聚集在电池单体内部， 导致蓄电池工作温度升高， 从而使得蓄电池过热。 由于阀控式铅酸蓄电池这一特点， 其更广泛应用受到一 定的限制。
事实上，阀控式铅酸蓄电池的过热主要来源于两部分：一部分是化学放热。 化学放热非常剧烈， 充电时仅氧复合反应就达到 68. 32kcal/mol， 所以电池在反 复充放电过程中， 放热速率极高， 很容易达到 80°C以上， 以至于过热； 另外一 部分热来源于欧姆热（由电池的栅板、汇流排、隔膜、端极柱等产生的电阻热）。 由于热量是从内部产生的， 而电池单体的外壳一般是由高分子材料制成， 热量 虽然可以从栅板、 汇流排、 端极柱等金属质地的电池组成部分散出， 但是散热 面积非常有限， 所以电池单体内部的热量不容易散出。
对于蓄电池的大功率应用场合， 根据阿伦尼乌斯方程， 温度每升高 10°C， 任何化学反应的反应速率一般将增加 2倍。该经验法则适用于基于失效模式（化 学反应如腐蚀、 氧复合反应等） 得到的产品寿命， 特别是适用于铅酸蓄电池的 使用寿命。 根据文献 " IEEE Recommended Practice for Maintenance, Testing, and Replacement of Vented Lead-Acid Batteries for Stationary Applications, IEEE power engineering society, IEEE std 450™ -2002, 3 April 2003 (电气和电子工程师协会推荐的用于固定应用场合的通气式铅酸电 池的维修、测试和更换的操作惯例"， IEEE电力工程协会， IEEE标准 450™ -2002， 2003年 4月 3 日） 所公开的内容， 计算得出， 电池工作温度从 25°C升高到 33 °C， 寿命缩短 50%。 为了防止蓄电池及其系统过热并延长其使用寿命， 目前已提出多种用于在 蓄电池工作时对其进行热控制或热管理的解决方案。 其中大部分解决方案是基 于电池单体侧面或底部的热控制或热管理，如专利文献 US7967256、US7531270、 US6533031 , US6512347 , US6407553、 US5695891、 US5356735 , US5385793、 US4913985中所描述的。此类改进设计大部分都是内置式的， 其维修和散热仍存 在技术上的问题。 上面已经论述过， 阀控式铅酸蓄电池内部所产生的热不容易 传递到电池外部， 因此， 如果将所述现有技术中的热控制或热管理方法应用于 阀控式铅酸蓄电池， 散热效果并不能非常令人满意。
US7651811公开了一种牵引用蓄电池，该蓄电池包括具有通风孔的用于覆盖 电连接条的塑料盖。 其中风扇迫使空气流动通过蓄电池的电连接条， 从而用于 降低蓄电池的工作温度。 US3834945则公开了利用水冷却牵引用蓄电池的端极柱 和电池单体间的电连接条。 无论是用空气冷却还是用水冷却， 由于电连接条的 换热面积有限， 因此， 换热效果的提高都不是非常明显。 此外， 所述具有冷却 蓄电池功能的结构设计， 例如增设水冷系统或风扇等， 往往使蓄电池整体结构 更为复杂、 体积大且笨重， 并且导致维修和安装工序复杂。
CN200952916Y公开了一种散热装置的改良结构， 该结构用于改善机械设备 在运转时所产生的机械热的散热效率， 其中， 在机器散热片外部以物理方式附 着一纳米碳层， 凭借增加整体散热面积和纳米碳层的快速散热特性， 提高散热 装置的散热效果。 但该文献未具体公开纳米碳层的有效组成， 更未教导、 或提 示所述纳米碳层用于其它领域。 目前还没有发现将散热涂层、 尤其是高辐射率 散热涂层应用到储能系统、 例如阀控式铅酸蓄电池及其系统中， 以解决储能系 统过热问题的报道。
上述文献在此全文引入以作参考。
因此， 本发明致力于对现有技术中的上述缺陷进行一处或多处改进。 发明内容 本发明目的在于提供一种防止自身过热的储能系统和防止储能系统过热的 方法， 从而使得储能系统具有良好的散热效果， 避免其在高功率充放电的条件 下工作温度过高， 从而延长其使用寿命， 并且本发明储能系统不存在安装繁琐 复杂的问题。
本发明另一目的是提供一种在储能系统或构成储能系统组件的至少部分外 表面上形成至少一层高辐射率散热涂层的方法。 上述目的可通过具有如下特征的储能系统来实现： 该储能系统包括散热的 外表面，其中，所述外表面的至少一部分上涂覆有至少一层高辐射率散热涂层。
有利地， 所述外表面包括储能系统本身、 构成储能系统的储能单元、 储能 单元之间的电连接件 （条） 、 储能单元的端极柱、 或支撑体的外露表面。 通过 在例如端极柱和 /或电连接件外表面的外露散热表面上涂覆高辐射率散热涂层， 同时以辐射、 对流、 和 /或导热的散热方式， 加快热量从所述散热表面向周围环 境的传递和扩散， 进而使得如端极柱和 /或电连接件等外表面的外露散热表面的 温度快速降低， 特别是， 由于端极柱和 /或电连接件具有自储能单元内部向外部 导热的作用， 端极柱和 /或电连接件等外表面温度的快速降低， 可以进一步降低 储能单元内部的温度， 因此， 通过这种方式， 有效降低了储能系统的工作温度， 并延长了储能系统的使用寿命。
在本发明一个优选实施例中， 所述高辐射率散热涂层含有纳米粒子或类似 物。 所述纳米粒子或类似物的实例为碳纳米管、 纳米棒、 纳米微球、 纳米颗粒 等。 在涂料中掺杂本身具有高辐射率的纳米粒子或类似物， 例如、 碳纳米管更 有利于提高涂层的热辐射率。 有利地， 所述纳米粒子或类似物的粒度小于 100 纳米。
为了有利于储能系统散热， 所述高辐射率散热涂层具有在 300K温度下大于 0. 8的黑体辐射率和大于 150W/m · Κ的导热率。优选地， 高辐射率散热涂层包括 各种氧化物， 例如 Si02、 Zr02、 Cr02、 A1203， 和 /或各种碳化物， 例如 ZrC、 SiC， 和 /或各种氮化物， 例如 Si3N4。 有利地， 当所述高辐射率散热涂层包括至少两层时， 各层的涂料组成、 厚 度、 或固化温度和时间可以相同或不同。 例如， 所述各涂层厚度小于或等于 200-300微米。 在储能系统外露散热表面上涂覆或形成掺杂有纳米粒子或类似物、 例如碳 纳米管的高辐射率散热涂层时， 可在同一表面上形成一层或多层高辐射率散热 涂层， 因此， 涂料可进行一次或多次涂覆， 每一涂层可在等于或高于室温的温 度下、 例如 50°C下固化。 此外， 为了进一步提高散热效果， 优选地， 高辐射率 散热涂层的层数可为 2、 3、 或 4。 即在储能系统外露散热表面上、 例如在端极 柱和 /或电连接件 （条） 外露散热表面上分两步-四步涂覆高辐射率散热涂料。 通过高辐射率散热涂层， 散热表面的散热效果和散热速度明显提高。
所述储能系统可以为蓄电池及其系统， 尤其是阀控式铅酸蓄电池及其系统。 另一方面， 本发明提供一种防止储能系统过热的方法， 所述储能系统包括 散热的外表面， 其中， 在所述外表面的至少一部分上形成或涂覆至少一层高辐 射率散热涂层。
又一方面， 本发明提供一种在储能系统或构成储能系统组件的至少部分外 表面上涂覆或形成至少一层高辐射率散热涂层的方法，依次包括以下步骤： （1 ) 混合所述涂层的有效组分或其前体， 搅拌至形成均匀涂料混合物； （2 ) 将上述 均匀涂料混合物涂覆在上述至少部分外表面上形成均质的涂层； （3 ) 在等于或 高于室温的固化温度下固化所述涂层直至完全固化； （4) 任选地， 依次重复上 述步骤 （1 ) 、 (2 ) 、 和 （3 ) ， 从而在上述至少部分外表面上形成多层高辐射 率散热涂层。
有利地， 用上述方法在上述至少部分外表面上涂覆或形成多层高辐射率散 热涂层， 例如 2-4层。 通过多层涂层的重叠布置， 可在层与层之间引入更多的 界面、 微裂纹、 和或微孔， 形成更有利于提高整个涂层辐射率的结构。
有利地， 所述各涂层的固化温度为 40°C-100°C、 例如为 50°C。 在该范围内 选择固化温度， 可能有利于形成具有大量气孔和微裂纹的涂层， 这样能够进一 步强化热辐射效果。
在所述储能系统外露散热表面、 如端极柱和 /或电连接条的外表面上形成或 涂覆高辐射率散热涂层、 例如掺有碳纳米管的散热涂层， 这赋予了储能系统外 露散热表面高辐射率特性， 这种特性强化了所述散热表面与周围环境之间的热 交换，从而有利于快速冷却所述散热表面，进而降低所述储能系统的工作温度， 延长储能系统的使用寿命。
附图说明 参考本说明书中构成本说明书一部分的附图描述本发明的示例性实施例， 附图与说明书一同用于解释本发明原理。 其中， 在附图中， 图 1是现有储能系统、 例如蓄电池系统的整体示意图；
图 2 是现有储能系统、 例如蓄电池系统用于连接电池单元 （储能单元） 端 极柱的电连接条 （件） 的示意图。
图 3a-3c是一侧涂覆有一层分别在室温、 50°C、和 100°C下固化的高辐射率 散热涂层的电连接条与传统没有涂覆高辐射率散热涂层的电连接条散热能力的 对比曲线图；
图 4是两侧都涂覆有一层在室温下固化的高辐射率散热涂层的电连接条与 传统没有涂覆高辐射率散热涂层的电连接条散热能力的对比曲线图；
图 5a-5b 是一侧分别涂覆有两层和三层在室温下固化的高辐射率散热涂层 的电连接条与传统没有涂覆高辐射率散热涂层的电连接条散热能力的对比曲线 图；
图 5c是两侧各涂覆有两层在 50°C下固化的高辐射率散热涂层的电连接条与 传统没有涂覆高辐射率散热涂层的电连接条散热能力的对比曲线图；
图 5d是两侧各涂覆有三层在 50°C下固化的高辐射率散热涂层的电连接条与 传统没有涂覆高辐射率散热涂层的电连接条散热能力的对比曲线图
图 6a是连接有一个两侧各涂覆有两层在 50°C下固化的高辐射率散热涂层的 电连接条的蓄电池与连接有一个两侧都没有涂覆高辐射率散热涂层的电连接条 的传统蓄电池的负极端极柱散热能力的对比曲线图；
图 6b是连接有一个两侧各涂覆有两层在 50°C下固化的高辐射率散热涂层的 电连接条的蓄电池与连接有一个两侧都没有涂覆高辐射率散热涂层的电连接条 的传统蓄电池的正极端极柱散热能力的对比曲线图。
具体实 li^r式
图 1 是现有储能系统 （通常指电能储存系统） 一个实施例的示意图。 该储 能系统可是蓄电池及其系统、 电容器及其系统、 或其它化学或物理储能装置。 下面以蓄电池系统为例进行说明。蓄电池系统 1包括多个电池单元（储能单元）
10。 每个电池单元 10可具有一个或多个电池单体 （储能单体） 。 所述多个电池 单元 10可以任何阵列方式排列。 每个电池单元 10具有自内部向外引出的两个 端极柱 101 (正极端极柱） 和 102 (负极端极柱） 。 各电池单元 10之间的电连 接通过电连接条 （件） 13来实现。 电连接条 13—端与一个电池单元 10的正极 端极柱 101连接， 另一端与另一电池单元 10的负极端极柱 102连接。 电连接条 13 由导电材料制成， 其用于在电池单元 10 之间传导电流。 蓄电池系统 1还包 括用于与外电路实现电连接的端极柱 （极柱） 即正极极柱和负极极柱。
如图 2所示， 传统电连接条 13是具有光滑表面的扁平板， 在电连接条 13 两端具有用于连接端极柱的连接孔 131、 132。 在本发明实施例中， 电连接条 13 由铜制成， 其尺寸为 85毫米 （长） X 30毫米 （宽） X 2毫米 （厚） 。 在蓄电池及其系统充放电过程中会产生大量热。 端极柱、 电连接条、 金属 栅板等部件由于其结构特点， 构成使热量从蓄电池单元 10内部空间向外传导和 扩散的热导体。 在本发明一个实施例中， 在端极柱和 /或电连接条外露散热表面 上形成或涂覆有一层或多层高辐射率散热涂层， 所述散热涂层由高辐射率散热 涂料形成。
所述高辐射率散热涂料包括各种氧化物、 例如 Si02、 Zr02、 Cr02、 A1203， 和 /或各种碳化物、 例如 ZrC、 SiC ， 和 /或各种氮化物、 例如 Si3N4。 目前， 所 述高辐射率散热涂料已被报道广泛应用在宇航飞船、锅炉、烤炉等机械设备上。
本文中 "高辐射率散热涂层"指在较宽的波长范围 （例如 1_20μ m) 内具有 比待被涂覆表面辐射率高的辐射率的涂层。
在本发明一个优选实施例中， 所述高辐射率散热涂料包含或掺杂有纳米粒 子或类似物。 在本文中， 含有纳米粒子或类似物的涂料称为纳米涂料， 其所形 成的涂层称为纳米涂层。 更优选地， 所述纳米粒子或类似物的粒度小于 100纳 米。 在本发明另一个实施例中， 所述纳米粒子或类似物的实例为碳纳米管、 纳 米棒、 纳米微球、 或纳米颗粒等。 在本文中， 含有碳纳米管的涂料称为碳纳米 管涂料， 其所形成的涂层称为碳纳米管涂层。
所述涂料或涂层的辐射率主要取决于其组成， 并对涂层本身的结构和其所 附着的表面的表面状态非常敏感。 影响涂层辐射率的因素包括涂料掺杂度、 涂 层表面粗糙度和 /或表面纹理、 涂层厚度等。 碳纳米管具有碳 -碳化学键、 高辐 射率、 良好的导热性、 高强度和较大的比表面积。 向涂料中掺杂碳纳米管不仅 能提高涂层拉伸强度和断裂韧度， 而且还可在碳纳米管和涂料基体之间提供大 量的新界面， 导致在涂层内部发生更多的电磁波反射， 因此， 能更多地吸收电 磁波形式的热量。 这是因为根据基尔霍夫定律， 对应于一定的波长和温度， 在 热平衡条件下，物体的辐射热流等于其吸收热流，所以， 吸收热量越多的物体， 辐射的热量也越多。 因此， 在高辐射率散热涂料中掺杂碳纳米管可使涂层的辐 射率显著地提高。
有利地， 所述高辐射率散热涂料或涂层具有在 300K温度下大于 0. 8的黑体 辐射率和大于 150W/m · K的导热率。 根据本发明， 在例如电连接条和 /或端极柱的外表面的外露散热表面上形成 或涂覆高辐射率散热涂层， 可以加速热量从所涂覆表面向周围环境扩散。 原因 在于， 涂层自身的高辐射率将有助于提高涂层所在表面的辐射率， 此外， 从微 观的角度而言， 涂覆含有纳米颗粒的涂层使得例如电连接条和 /或端极柱的外表 面变得粗糙， 从而增大了整个储能系统的外露散热表面， 进而增加了电磁波的 反射。 由此导致热量快速从例如电连接条和 /或端极柱的外表面向周围环境辐射 和扩散能量， 从而降低了端极柱外露表面的温度。 此外， 由于端极柱构成自电 池单元内部向外的热扩散通道， 因此， 端极柱位于电池单元内部的部分与外露 部分的温差加大， 从而导致热量快速从电池单元内部向电连接条和 /或端极柱的 外露表面传导和扩散， 因此， 整体而言， 能够快速将热量从电池单元内部向外 部环境导出， 从而降低蓄电池及其系统的工作温度， 延长蓄电池的使用寿命。
上述高辐射率散热涂层各层的厚度优选小于或等于 200-300微米。
在本发明又一个具体实施例中， 通过多步、 例如两步-四步涂覆工艺， 在电 连接条和 /或端极柱的外露表面上形成或涂覆多层、 例如两层-四层高辐射率散 热涂层， 其中， 每层涂料的涂覆过程包括如下步骤： （1 ) 混合所述高辐射率散 热涂料的有效组分或其前体， 搅拌至形成均匀涂料混合物； （2 ) 将均匀涂料混 合物涂覆在所述外表面上形成均质的涂层； （3 )在室温或高于室温的固化温度 下固化上述均质涂层直至完全固化，例如烘烤 4-24小时。在上述涂料混合物中， 也可以含有溶剂和 /或提高涂料粘接力的胶结剂。 当所述高辐射率散热涂层为至 少两层时， 每层的固化温度和固化时间可以相同或不同。 在上述涂覆工艺的固 化过程中， 快速升温能将所形成的气体封闭在所述涂层内部， 从而可能形成气 孔、 微界面、 和 /或微裂纹， 这将有利于形成具有更多用于反射电磁波的界面的 多孔层， 因此， 能够获得更好的吸收和辐射特性。 优选地， 所述高辐射率散热 涂层各层的固化温度为 40°C-100°C， 例如 50°C。 此外， 当所述高辐射率散热涂 层为至少两层时， 不同涂层之间重叠布置使得涂层之间引入了额外的界面， 从 而又有可能产生更多有利于反射的的微裂纹、 气孔、 和 /或微界面层， 这将更有 利于提高整个涂层的辐射率， 加快热量从被涂覆表面向外扩散和传递。 根据本发明， 在上述外表面上形成或涂覆多层高辐射率散热涂层时， 各涂 层的涂料组成、 厚度、 固化温度和固化时间可以相同或不同。 下面以扁平状的电连接条 （件） 为例， 对传统电连接条和本发明涂覆有碳 纳米管涂层 （含有碳纳米管的高辐射率散热涂层） 的电连接条散热能力或蓄热 能力进行对比。 其中所述碳纳米管涂层为商购的志盛涂料 ZS-411型。 为了模拟 不同电连接条吸收等值热量后本身的温度变化， 首先， 提供一个固定的热源 ( 200W) ， 将等量的热流通过传统电连接条和本发明电连接条， 利用热电偶实 时测量电连接条的表面温度。 其中针对不同涂层和不同涂覆条件， 在大约 1500 秒的时间范围内测定上述两种电连接条的表面温度， 并进行对比。 实验发现本 发明电连接条的表面温度显著低于传统电连接条的表面温度， 这说明本发明电 连接条散热能力远大于传统电连接条散热能力。
根据本发明， 可在室温 -ioo°c的温度范围内选择固化涂层的温度 （即固化 温度） 。 为了选择合适的固化温度， 对涂覆有在不同温度下固化的涂层的电连 接条与传统没有涂覆高辐射率散热涂层的电连接条的散热能力进行对比。 如图 3a-3c所示， 对一侧涂覆有一层分别在室温、 50°C、 和 100°C下固化的碳纳米管 涂层的电连接条进行实验， 结果发现： 在固化温度为室温 （约 20 °C ) 时， 本发 明电连接条与传统电连接条的最大表面温差为 19. 4°C， 如图 3a所示； 在固化温 度为 50 °C时， 本发明电连接条与传统电连接条的最大表面温差为 31. 0 °C， 如图 3b所示； 在固化温度为 100 °C时， 本发明电连接条与传统电连接条的最大表面 温差为 26. 1 °C， 如图 3c所示。 因此， 针对碳纳米管涂层， 优选地， 所述固化温 度约为 50°C。 理论上讲， 在所述外露散热表面上形成或涂覆的涂层面积越大， 散热速度 越快。 为了证实是否涂层面积越大散热越快， 对涂覆有在相同温度 （在本次实 验中固化温度为室温） 下固化、 但涂覆面积不同的涂层的电连接条与传统没有 涂覆高辐射率散热涂层的电连接条的散热能力进行对比。 图 3a是一侧涂覆有一 层在室温下固化的碳纳米管涂层的电连接条与传统电连接条的表面温度对比， 本发明电连接条与传统电连接条的最大表面温差为 19. 4°C。 图 4是两侧各涂覆 有一层在室温下固化的碳纳米管涂层的电连接条与传统电连接条的表面温度对 比，本发明电连接条与传统电连接条的最大表面温差为 53. 8°C。因此，优选地， 在储能系统、 例如蓄电池及其系统的电连接条两侧都形成或涂覆由含纳米粒子 或类似物的涂料形成的高辐射率散热涂层。
此外， 对涂覆有分别在室温和 50 °C下固化、 涂覆层数不同的碳纳米管涂层 的电连接条与传统没有涂覆高辐射率散热涂层的电连接条的散热能力进行了对 比。 图 5a是一侧涂覆有两层在室温下固化的碳纳米管涂层的电连接条与传统没 有涂覆高辐射率散热涂层的电连接条的散热能力对比， 本发明电连接条与传统 电连接条的最大表面温差为 26. 9°C ;图 5b是一侧涂覆有三层在室温下固化的碳 纳米管涂层的电连接条与传统没有涂覆高辐射率散热涂层的电连接条的散热能 力对比， 本发明电连接条与传统电连接条的最大表面温差为 37. 5 °C。 通过分析 图 5a和图 5b的结果， 可以发现在固化温度为室温时， 电连接条一侧涂覆的碳 纳米管涂层层数越多， 散热能力越强。
当固化温度为 50 °C时， 如图 5c所示， 在两侧各涂覆有两层碳纳米管涂层的 电连接条与传统没有涂覆高辐射率散热涂层的电连接条的最大表面温差为 51. 9 °C ; 同样， 如图 5d所示， 在两侧各涂覆有三层碳纳米管涂层的电连接条与传统 没有涂覆高辐射率散热涂层的电连接条的最大表面温差为 46. 4°C。 因此， 优选 地， 在 50°C的固化温度下， 在电连接条两侧上各涂覆有两层碳纳米管涂层。 与此同时， 对连接有一个涂覆碳纳米管涂层的本发明电连接条的阀控式铅 酸蓄电池和连接有一个未涂覆碳纳米管涂层的电连接条的传统阀控式铅酸蓄电 池的散热能力进行对比， 所用阀控式铅酸蓄电池均为 Leoch DJ100。 其中， 连接 到阀控式铅酸蓄电池上的本发明电连接条在两侧各涂覆有两层在 50°C下固化的 碳纳米管涂层。 为了模拟不同蓄电池在吸收等值热量后的放热情况， 首先， 将 所述蓄电池在一定温度下在加热炉内加热直到达到稳定状态， 接着自然冷却蓄 电池， 期间利用热电偶对电池的不同部位进行温度测量。 实验发现， 与传统蓄 电池相比， 本发明蓄电池的温度 （典型地， 正极端极柱和负极端极柱的温度） 以更快的速度降低， 在 7分钟内产生了 3-4°C的温降， 比传统蓄电池快 16%, 如 图 6a和 6b所示， 其中图 6a是蓄电池负极端极柱的温度变化对比图， 图 6b是 蓄电池正极端极柱的温度变化对比图。 根据本发明， 在所述储能系统中， 所述可涂覆高辐射率散热涂层的表面不 仅仅局限于端极柱和 /或电连接条的外表面， 而且也可包括所述储能系统、 构成 储能系统组件的外表面、 或储能系统或其组件的支承结构的外表面等。 对于通 常在高功率和持续运行条件下工作的具有多个端极柱和 /或电连接条的储能系 统， 所述在至少部分外露散热表面上形成或涂覆至少一层高辐射率散热涂层的 方法具有更好的适用价值， 并且能更有效地降低储能系统的工作温度。 所述在至少部分外露散热表面上形成或涂覆至少一层高辐射率散热涂层的 方法可以单独使用或结合其它强化散热的现有技术一起使用， 例如增设风扇以 加强外露散热表面的对流散热。
需要说明的是， 电连接条或端极柱本身的电阻极小。 在涂覆有高辐射率散 热涂层、 例如碳纳米管涂层的情况下， 电连接条和 /或端极柱的电阻热的变化可 以忽略不计。
以上所述仅为本发明的优选实施例， 并不用于限制本发明， 对本领域技术 人员而言， 可以在不偏离本发明范围的情况下对本发明系统和方法做出多种改 良和变型。 本领域技术人员通过参考本说明书中公开的内容也可得到其它实施 例。 本说明书和实施例仅应被视为示例性的， 本发明的真实范围由所附权利要 求以及等同方案限定。

Claims

权利要求书
1. 一种防止自身过热的储能系统， 包括散热的外表面， 其特征在于： 所 述外表面的至少一部分上涂覆或形成有至少一层高辐射率散热涂层。
2. 根据权利要求 1所述的储能系统， 其中， 所述外表面包括： 储能系统 本身、 构成储能系统的储能单元、 储能单元之间的电连接件、 储能单元的端极 柱、 或支撑体的外露表面。
3. 根据权利要求 1所述的储能系统 ， 其中， 所述高辐射率散热涂层含有 纳米粒子或类似物。
4. 根据权利要求 3所述的储能系统， 其中， 所述纳米粒子或类似物为碳 纳米管。
5. 根据权利要求 3所述的储能系统，其中，所述纳米粒子的粒度小于 100 纳米。
6. 根据权利要求 1所述的储能系统， 其中，所述高辐射率散热涂层在 40 °C-100°C下固化。
7. 根据权利要求 6所述的储能系统， 其中，所述高辐射率散热涂层在 50 下固化。
8. 根据权利要求 1-7任何之一所述的储能系统， 其中， 所述高辐射率散 热涂层具有在 300K温度下大于 0. 8的黑体辐射率和大于 150W/m · K的导热率。
9. 根据权利要求 1-7任何之一所述的储能系统， 其中， 所述高辐射率散 热涂层每层厚度小于或等于 200-300微米。
10. 根据权利要求 1-7任何之一所述的储能系统， 其中， 所述高辐射率散 热涂层各层的涂料组成、 厚度、 或固化温度和时间相同或不同。
11. 根据权利要求 9所述的储能系统， 其中， 所述高辐射率散热涂层的层 数为 2、 3、 或 4。
12. 根据权利要求 1-7和 11任何之一所述的储能系统， 其中， 所述储能 系统为阀控式铅酸蓄电池或其系统。
13. 一种防止储能系统过热的方法， 所述储能系统包括散热的外表面， 其 特征在于： 在所述外表面的至少一部分上涂覆或形成至少一层高辐射率散热涂 层。
14. 根据权利要求 13所述的方法， 其中， 所述外表面包括： 储能系统本 身、构成储能系统的储能单元、储能单元之间的电连接件、储能单元的端极柱、 或支撑体的外露表面。
15. 根据权利要求 13所述的方法， 其中， 所述高辐射率散热涂层含有纳 米粒子或类似物。
16. 根据权利要求 15所述的方法， 其中， 所述纳米粒子或类似物为碳纳 米管。
17. 根据权利要求 15所述的方法， 其中， 所述纳米粒子的粒度小于 100 纳米。
18. 根据权利要求 16所述的方法， 其中， 在 40°C-100°C下固化所述高辐 射率散热涂层。
19. 根据权利要求 18所述的方法， 其中， 在 50°C下固化所述高辐射率散 热涂层。
20. 根据权利要求 13-19任何之一所述的方法， 其中， 所述高辐射率散热 涂层具有在 300K温度下大于 0. 8的黑体辐射率和大于 150W/m · K的导热率。
21. 根据权利要求 13-19任何之一所述的方法， 其中， 所述高辐射率散热 涂层每层厚度小于或等于 200-300微米。
22. 根据权利要求 13-19任何之一所述的方法， 其中， 所述高辐射率散热 涂层各层的涂料组成、 厚度、 或固化温度和时间相同或不同。
23. 根据权利要求 21所述的方法， 其中， 所述高辐射率散热涂层的层数 为 2、 3、 或 4。
24. 根据权利要求 13-19和 23任何之一所述的方法， 其中， 所述储能系 统为阀控式铅酸蓄电池或其系统。
25. 一种在储能系统或构成储能系统组件的至少部分外表面上涂覆或形 成至少一层高辐射率散热涂层的方法， 依次包括以下步骤：
( 1 ) 混合所述涂层的有效组分或其前体，搅拌至形成均匀涂料混合物; (2) 将均匀涂料混合物涂覆在上述至少部分外表面上形成均质的涂 层；
(3) 在等于或高于室温的固化温度下固化所述涂层直至完全固化。
(4) 任选地， 依次重复上述步骤 （1) 、 (2) 、 和 （3) ， 从而在上 述至少部分外表面上形成多层高辐射率散热涂层。
26. 根据权禾 ί要求 25所述的方法， 其中， 所述高辐射率散热涂层含有纳 米粒子或类似物。
27. 根据权禾 ί要求 26所述的方法， 其中， 所述纳米粒子或类似物为碳纳
28. 根据权禾 ί要求 27所述的方法， 其中， 所述高辐射率散热涂层固化温 度为 40°C-100°Co
29. 根据权禾 ί要求 28所述的方法， 其中， 所述高辐射率散热涂层固化温 度进一步为 50°C。
30. 根据权禾 ί要求 25-29任何之
涂层厚度小于或等于 200-300微米。 1要求 25-29任何之
Figure imgf000016_0001
为 2、 3、 或 4。
PCT/CN2012/074434 2012-04-20 2012-04-20 防止自身过热的储能系统、防止储能系统过热的方法、和在储能系统上形成散热涂层的方法 WO2013155700A1 (zh)

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