CN115133195B - 一种金属电池盒防火涂层的制备方法及金属电池盒 - Google Patents

一种金属电池盒防火涂层的制备方法及金属电池盒 Download PDF

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CN115133195B
CN115133195B CN202210895475.6A CN202210895475A CN115133195B CN 115133195 B CN115133195 B CN 115133195B CN 202210895475 A CN202210895475 A CN 202210895475A CN 115133195 B CN115133195 B CN 115133195B
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coating
metal battery
battery box
fireproof coating
gun
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CN115133195A (zh
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冯晶
汪俊
潘洪江
利建雨
张宇轩
宋建博
苏涛
张陆洋
李振军
张艳宝
王峰
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Shaanxi Tianxuan Coating Technology Co ltd
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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
    • 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
    • H01M50/218—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material
    • H01M50/22—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks
    • H01M50/231—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by the material of the casings or racks having a layered structure
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    • B32B19/00—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica
    • B32B19/06—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica next to a fibrous or filamentary layer
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
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    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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    • C—CHEMISTRY; METALLURGY
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
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Abstract

本发明公开了一种金属电池盒防火涂层的制备方法及金属电池盒，在金属电池盒外表面依次制备金属粘结层和稀土钽酸盐热障涂层；在稀土钽酸盐热障涂层上包覆第一纤维棉层；其中，第一纤维棉层外表面涂有防火涂层；采用粘结剂在防火涂层上包覆第二纤维棉层；本发明通过在金属电池盒外表面制备稀土钽酸盐热障涂层，并结合两层纤维棉以及防火涂层，大大地提升了隔热效果，且可以避免金属电池盒的氧腐蚀和水腐蚀，避免了氧气进入电池盒，进而防止高温自燃的发生。

Description

一种金属电池盒防火涂层的制备方法及金属电池盒
技术领域
本发明属于新能源汽车的电池盒技术领域，尤其涉及一种金属电池盒防火涂层的制备方法及金属电池盒。
背景技术
传统电动汽车金属电池盒的材料多采用钢材或铝材，通过冲压、焊接或铸造的加工方式获得。作为电池总成之一的电池盒是电池的承载和保护装置。电池盒内的热失控会导致其内部发生短路，从而引起电池正负极材料发生剧烈化学反应，导致电芯温度急剧上升、压力过大、外壳破裂、整车自燃起火甚至爆炸等事故。
目前动力电池已经采取了很多的安全措施来尽量避免事故的发生，如通过电池结构设计、提高壳体材料防火性能、改善电池散热系统等等。此外，铺设防火毡材料为主要防火渠道，当电池发生热失控后，依靠防火毡材料可以有效隔绝热量扩散和控制火势走向，延缓电池热扩散时间，从而提高电池包防火安全性。防火毡贴敷在电池盒上盖外表面，以减缓电池盒热扩散时对乘员舱的热量传递。
虽然防火毡可以隔绝热量扩散、控制火势走向和延缓电池热扩散。但增加防火毡方案隔热效果仍较差，且也存在质量增加和设计施工过程中局限性大等问题
发明内容
本发明的目的是提供一种金属电池盒防火涂层的制备方法及金属电池盒，以进一步提升金属电池盒的隔热效果。
本发明采用以下技术方案：一种金属电池盒防火涂层的制备方法，包括以下步骤：
在金属电池盒外表面依次制备金属粘结层和稀土钽酸盐热障涂层；
在稀土钽酸盐热障涂层上包覆第一纤维棉层；其中，第一纤维棉层外表面涂有防火涂层；
采用粘结剂在防火涂层上包覆第二纤维棉层；
其中，防火涂层的制备方法为：
将氧化钙在去离子水中搅拌、分散均匀后得到固化剂；
称取稀土钽酸盐、氧化锆、二氧化硅、二氧化钛、氢氧化铝、玻璃粉和粘结剂，在搅拌机中搅拌均匀后与固化剂混合，再次搅拌均匀后，将其涂在第一纤维棉层上。
进一步地，采用超音速火焰喷涂在金属电池盒外表面制备金属粘结层；
金属粘结层的成分为NiCrAlY或CoCrAlY或NiCoCrAlY，球形率>97％，流动性为20～60s/50g，厚度为40～80μm；
超音速火焰喷涂方法的参数为：
金属电池盒的外表面温度为150～200℃，x轴喷枪枪速50～600mm/s，y轴喷枪枪速50～450mm/s，喷枪步距为5～12mm，喷枪枪距为0～360mm，燃烧室压力为0～160Pa，送粉速度为4～10rpm，氧气流量为500～1800scfh，载气流量为0～25scfh，进水温度为0～30℃，回水温度不高于50℃。
进一步地，稀土钽酸盐热障涂层以YTaO4为原料，采用大气等离子喷涂方法制备；
YTaO4的球形率>97％，流动性为20～45s/50g，其在900℃的热导率为1.1～1.4Wm- 1k-1；
稀土钽酸盐热障涂层厚度为100～150μm；
大气等离子喷涂方法的参数为：
金属电池盒的外表面温度为150～250℃，x轴喷枪枪速为1000～1800mm/s，y轴喷枪枪速为200～400mm/s，喷枪步距为5～10mm，喷枪枪距为100～220mm，系统电压为200～260V，电流为300～550A，功率为70～150W，送粉速度为5～8rpm，氩气流量为100～200scfh，氢气流量为20～60scfh，氮气流量为60～210scfh，载气流量为0～40scfh。
进一步地，氧化钙和去离子水的质量比为1：(1～3)，搅拌速率为100～600r/min，搅拌时间为30～90min。
进一步地，稀土钽酸盐、氧化锆、二氧化硅、二氧化钛、氢氧化铝、玻璃粉和粘结剂的质量比为(1～3)：(1～2)：(1～2)：(1～2)：(1～2)：(1～2)：(3～6)，搅拌速率为100～600r/min，搅拌时间为60～120min。
进一步地，参与混合的固化剂占防火涂层材料总质量的1～3％，且混合时搅拌速率为100～600r/min，搅拌时间为60～120min；
防火涂层的厚度为5～15mm，常温下固化20～120h。
本发明的另一种技术方案：一种金属电池盒，其外表面具有防火涂层，防火涂层采用上述的一种金属电池盒防火涂层的制备方法制成。
进一步地，电池盒上设置有导热铜条，导热铜条在一部分位于金属电池盒的内部空间，另一部分依次穿过金属电池盒和防火涂层后位于金属电池盒的外部空间。
进一步地，还包括风冷装置，风冷装置朝向位于外部空间的导热铜条。
本发明的有益效果是：本发明通过在金属电池盒外表面制备稀土钽酸盐热障涂层，并结合两层纤维棉以及防火涂层，大大地提升了隔热效果，且可以避免金属电池盒的氧腐蚀和水腐蚀，避免了氧气进入电池盒，进而防止高温自燃的发生。
附图说明
图1为本发明实施例中电池盒涂层结构示意图；
图2为本发明实施例1中防火涂层和金属电池盒基体在100～900℃的热导率效果图；
图3为本发明实施例1、对比例1和实施例2中的金属电池盒热考核温度曲线对比图；
图4为本发明实施例3和实施例4中的金属电池盒热考核温度曲线对比图。
其中，1.电池盒本体；2.金属粘结层；3.稀土钽酸盐热障涂层；4.第一纤维棉层；5.防火涂层；6.第二纤维棉层。
具体实施方式
下面结合附图和具体实施方式对本发明进行详细说明。
本发明公开了一种金属电池盒防火涂层的制备方法，包括以下步骤：在金属电池盒外表面依次制备金属粘结层和稀土钽酸盐热障涂层；在稀土钽酸盐热障涂层上包覆第一纤维棉层；其中，第一纤维棉层外表面涂有防火涂层；采用粘结剂在防火涂层上包覆第二纤维棉层。
其中，防火涂层的制备方法为：将氧化钙在去离子水中搅拌、分散均匀后得到固化剂；称取稀土钽酸盐、氧化锆、二氧化硅、二氧化钛、氢氧化铝、玻璃粉和粘结剂，在搅拌机中搅拌均匀后与固化剂混合，再次搅拌均匀后，将其涂在第一纤维棉层上。
本发明通过在金属电池盒外表面制备稀土钽酸盐热障涂层，并结合两层纤维棉以及防火涂层，大大地提升了隔热效果，且可以避免金属电池盒的氧腐蚀和水腐蚀，避免了氧气进入电池盒，进而防止高温自燃的发生。
在本实施例中，金属电池盒的材质为钢或铝或钛合金，这样，金属电池盒可以拥有较好的防爆、防冲击效果，具有较好的散热作用。
在对金属电池盒外表面进行处理之前，首先需要对其外表面进行预处理，该实施例中，用丙酮除去金属电池盒表面的污渍，再用喷砂设备喷涂一层30μm的刚玉砂，以使表面粗糙化。
接着，采用超音速火焰喷涂在金属电池盒外表面制备金属粘结层；金属粘结层的成分为NiCrAlY或CoCrAlY或NiCoCrAlY，球形率>97％，流动性为20～60s/50g，厚度为40～80μm。超音速火焰喷涂方法的参数为：
金属电池盒的外表面温度为150～200℃，x轴喷枪枪速50～600mm/s，y轴喷枪枪速50～450mm/s，喷枪步距为5～12mm，喷枪枪距为0～360mm，燃烧室压力为0～160Pa，送粉速度为4～10rpm，氧气流量为500～1800scfh，载气流量为0～25scfh，进水温度为0～30℃，回水温度不高于50℃。
金属的热膨胀系数一般为(13～18×10-6K-1)，而金属粘结层的热膨胀系数(11～14×10-6K-1)与陶瓷的热膨胀系数(10～12×10-6K-1)相近，因此，用金属粘结层作为过渡层，避免了稀土钽酸盐热障涂层与金属基体的热失配。
然后，在金属粘结层外部制备稀土钽酸盐热障涂层，该稀土钽酸盐热障涂层以YTaO4为原料，采用大气等离子喷涂方法制备；YTaO4的球形率>97％，流动性为20～45s/50g，其在900℃的热导率为1.1～1.4Wm-1k-1；稀土钽酸盐热障涂层厚度为100～150μm；
大气等离子喷涂方法的参数为：金属电池盒的外表面温度为150～250℃，x轴喷枪枪速为1000～1800mm/s，y轴喷枪枪速为200～400mm/s，喷枪步距为5～10mm，喷枪枪距为100～220mm，系统电压为200～260V，电流为300～550A，功率为70～150W，送粉速度为5～8rpm，氩气流量为100～200scfh，氢气流量为20～60scfh，氮气流量为60～210scfh，载气流量为0～40scfh。
稀土钽酸盐热障涂层的制备不仅有隔热的作用，还有效避免了金属电池盒的氧腐蚀和水腐蚀，也避免了氧气进入电池盒，温度过高时发生自然现象。
然后，在稀土钽酸盐热障涂层外部包覆第一纤维棉层，纤维棉为氧化铝纤维棉或玄武岩纤维棉或石棉，厚度为0.5～2cm。纤维棉的具有高度耐火性、电绝缘性和绝热性，是重要的防火、绝缘和保温材料，可有效隔绝热量，此外，纤维棉密度较低，有助于电池系统的轻量化。而且。纤维棉具有较高的熔点和韧性，可进一步起到防火作用和抵抗外部机械撞击造成涂层的开裂。
在第一纤维棉层外表面还涂有防火涂层。在防火涂层的制备过程中，氧化钙和去离子水的质量比为1：(1～3)，搅拌速率为100～600r/min，搅拌时间为30～90min。稀土钽酸盐、氧化锆、二氧化硅、二氧化钛、氢氧化铝、玻璃粉和粘结剂的质量比为(1～3)：(1～2)：(1～2)：(1～2)：(1～2)：(1～2)：(3～6)，搅拌速率为100～600r/min，搅拌时间为60～120min。
氧化钙分散后可以加速水玻璃的脱水和固化，提高工作效率。若将氧化钙同稀土钽酸盐、氧化锆、二氧化硅、二氧化钛、氢氧化铝和玻璃粉一起加入粘结剂中，则会导致浆料固化速度过快，还没搅拌均匀，浆料中的颗粒就会发生团聚并迅速固化，影响涂层的致密度和热力学性能。
优选的，稀土钽酸盐、氧化锆、二氧化硅、二氧化钛、氢氧化铝和玻璃粉的粒径为1～50μm。这是因为较小的粒径有助于涂层表面光滑、美观。
在本实施例中，稀土钽酸盐选用稀土钽酸钇，稀土钽酸钇具有较低的热导率(1.4～1.9W·m-1·K-1，900℃)，有助于提高涂层的热绝缘性，较小的杨氏模量(128～178GPa)和脆性指数，有助于提高涂层的抗损伤能力，较高的熔点，有助于提高涂层的防火温度。
氧化锆具有较高的韧性，提高涂层的结合强度和抗损伤型。二氧化硅和二氧化钛作为填充料，较高的熔点有助于提高涂层的耐火温度。氢氧化铝作为两性氢氧氧化物，可以作为涂层中的酸碱中和材料，也具有阻燃作用和粘性作用，提高涂层的防火性能和结合强度。玻璃粉熔点较低(300～500℃)，有助于在高温过程中愈合涂层中的空隙，提高涂层的密封性，降低电池盒周围的氧含量。水玻璃(粘结剂)是一种硅酸盐无机粘结剂，具有较强的粘结能力，硬化时析出硅酸凝胶，有堵塞毛细孔隙而防止水渗透的作用，同时具有较好的耐热性能和耐酸性能。
在本发明实施例中，参与混合的固化剂占防火涂层材料总质量的1～3％，且混合时搅拌速率为100～600r/min，搅拌时间为60～120min；防火涂层的厚度为5～15mm，常温下固化20～120h。
本发明还公开了一种金属电池盒，其外表面具有防火涂层，防火涂层采用上述的一种金属电池盒防火涂层的制备方法制成。
另外，电池盒上设置有导热铜条，导热铜条在一部分位于金属电池盒的内部空间，另一部分依次穿过金属电池盒和防火涂层后位于金属电池盒的外部空间。更具体的，还包括风冷装置，风冷装置朝向位于外部空间的导热铜条。导热铜条可以采用U型的形状，其与防火涂层之间密封处理。
具体的，U型导热铜条的直径优选为0.5～1cm，每隔1～1.2cm放置一匹U型导热铜条。U型导热铜条的热导率为390～400W/m/k，较高的热导率可有效将电池产生的热量带走，避免热量的集中导致电池起火，添加的风冷装置进一步降低了U型铜条末端的热量。本实施例的金属电池盒，具有散热、防火、灭火、耐高温综合效应，耐火温度高达1500℃，可有效解决电池盒的散热和防火问题。进一步解决新能源汽车因热量集中或外部热量导致电池起火的问题。
具体的，如图1所示，为金属电池盒的涂层结构示意图，其中，金属电池盒由内至外依次包括电池盒本体1、金属粘结层2、稀土钽酸盐热障涂层3、第一纤维棉层4、防火涂层5和第二纤维棉层6。
实施例1：
将45匹U型导热铜条(直径为0.5cm)镶嵌在金属电池盒上，每隔1.2cm放置一匹U型导热铜条，用丙酮除去金属电池盒表面的污渍，再用喷砂设备喷涂一层30±5μm的刚玉砂，以使表面粗糙化，接着用超音速火焰喷涂(HVOF)喷涂一层厚度为60±5μm的NiCrAlY粘结层，超音速火焰喷涂(HVOF)的x轴喷枪枪速400mm/s，y轴喷枪枪速350mm/s，喷枪步距8mm，喷枪枪距330mm，燃烧室压力128Pa，送粉4.5rpm，氧气流量1700scfh，载气流量23scfh，进水温度30℃，回水温度为45～50℃。
采用大气等离子喷涂的方法喷涂一层100μm的稀土钽酸钇YTaO4涂层，喷涂参数为：x轴喷枪枪速1700mm/s，y轴喷枪枪速400mm/s，喷枪步距8mm，喷枪枪距120mm，系统电压220V，电流422A，送粉速率为8rpm，氩气流量180scfh，氢气流量40scfh，氮气流量90scfh，载气流量40scfh。
在隔热涂层表面包覆第一纤维棉层，厚度为1.5cm。称取氧化钙2kg和去离子水3kg，在搅拌机中搅拌90min(搅拌速率为400r/min)。称取稀土钽酸钇2kg、氧化锆1.5kg、二氧化硅1kg、二氧化钛1kg、氢氧化铝1.5kg、玻璃粉1kg和水玻璃5kg，在搅拌机中搅拌90min(搅拌速率为400r/min)后倒入0.2kg固化剂，再次搅拌90min(搅拌速率为400r/min)后将其刷涂在纤维棉上制备防火涂层，涂层厚度为8mm，并将U型铜条的末端裸露在涂层外侧，并在裸露的铜条处安装一个风冷装置，常温固化60h后得到防火涂层。
以水玻璃为粘结剂，将第二纤维棉层粘接在防火涂层表面，厚度为10mm，待常温固化60h后得到金属电池盒防火涂层。
本发明由散热系统(即U型导热铜条)、隔热涂层、两层防火纤维棉层及其中间的防火涂层组成的耐高温防火涂层，总厚度为1.699cm。具有散热、防火、灭火、耐高温综合效应。
如图2所示，图2a为金属电池盒的热导率，图2b为防火涂层的热导率。可以看出，金属电池盒基体的热导率较高(34.5～50.1W·m-1·K-1)，防火涂层的热导率极低(0.072～0.2W·m-1·K-1)，可知带有防火涂层的金属电池盒具有更好的隔热性能。
对比例1：
该实施例与实施例1的区别在于基体不制备任何涂层，将纯金属基体在100～1100℃进行热考核实验。
实施例2：
该实施例与实施例1的区别在于基体底层纤维棉的厚度为1cm。
如图3所示，为在100～1100℃考核时的考核温度和背温曲线图，升温速率10℃/min，每个考核温度的保温时间为0.5min。
如图所示，考核温度为100～1100℃时，实施例1中带有防火涂层(第一纤维棉层厚度为1.5cm时)的背温为25～280℃，考核过程中无燃烧现象，表明防火涂层具有较好的隔热和防火性能。
相对于实施例1，对比例1中纯金属电池盒的基体，随着考核温度的升高，背温和考核温度比较接近，几乎没有温差，表明没有涂层的金属电池盒隔热、防火效果较差。实施例2中的具有防火涂层的金属电池盒随着考核温度的升高，相比于实施例1，背温升高，表明纤维棉厚度减少，隔热和防火效果降低。
实施例3：
将45匹U型导热铜条(直径为0.5cm)镶嵌在金属电池盒内测，每隔1.2cm放置一匹U型导热铜条，用丙酮除去金属电池盒表面的污渍，再用喷砂设备喷涂一层30±5μm的刚玉砂，以使表面粗糙化，接着用超音速火焰喷涂(HVOF)喷涂一层厚度为60±5μm的NiCrAlY粘结层，超音速火焰喷涂(HVOF)的x轴喷枪枪速400mm/s，y轴喷枪枪速350mm/s，喷枪步距8mm，喷枪枪距330mm，燃烧室压力128Pa，送粉4.5rpm，氧气流量1700scfh，载气流量23scfh，进水温度30℃，回水温度为45～50℃。
采用大气等离子喷涂的方法喷涂一层100μm的稀土钽酸钇YTaO4涂层，喷涂参数为：x轴喷枪枪速1700mm/s，y轴喷枪枪速400mm/s，喷枪步距8mm，喷枪枪距120mm，系统电压220V，电流422A，送粉速率为8rpm，氩气流量180scfh，氢气流量40scfh，氮气流量90scfh，载气流量40scfh。
将U型铜条的末端裸露在涂层外侧，并在裸露的铜条处安装一个风冷装置，本实施例耐高温防火涂层的总厚度为0.019cm。
实施例4：
本实施例与实施例3的区别在于没有喷涂金属粘结层和稀土钽酸盐热障涂层，直接在基体表层制备两层防火纤维棉层及其中间的防火涂层，具体为：
将45匹U型导热铜条(直径为0.5cm)镶嵌在金属电池盒内测，每隔1.2cm放置一匹U型导热铜条，用丙酮除去金属电池盒表面的污渍，再用喷砂设备喷涂一层30±5μm的刚玉砂，以使表面粗糙化，然后在表面包覆一层纤维棉，厚度为1.5cm。称取氧化钙2kg和去离子水3kg，在搅拌机中搅拌90min(搅拌速率为400r/min)。称取稀土钽酸钇2kg、氧化锆1.5kg、二氧化硅1kg、二氧化钛1kg、氢氧化铝1.5kg、玻璃粉1kg和粘结剂水玻璃5kg，在搅拌机中搅拌90min(搅拌速率为400r/min)后倒入0.2kg固化剂，再次搅拌90min(搅拌速率为400r/min)后将其刷涂在纤维棉上制备防火涂层，涂层厚度为8mm，并将U型铜条的末端裸露在涂层外侧，并在裸露的铜条处安装一个风冷装置，常温固化60h后得到防火涂层。以水玻璃为粘结剂，将纤维棉粘接在防火涂层表面，厚度为10mm，待常温固化60h后得到金属电池盒防火涂层。
本实施例由散热系统、两层防火纤维棉层及其中间的防火涂层组成的耐高温防火涂层，总厚度为1.68cm。
如图4所示，为在100～1100℃考核时的考核温度和背温曲线图，升温速率10℃/min，每个考核温度的保温时间为0.5min。实施例3中的金属电池盒在考核温度为100～1100℃时，背温为60～800℃，背温较高。实施例4中的金属电池盒在100～1100℃考核时背温为25～387℃，考核过程中无燃烧现象，相对于实施例3，背温降低，但仍然偏高。
另外，综合比较实施例1～4和对比例1，发现实施例1中的30μm刚玉砂+60μm的NiCrAlY粘结层+100μm的YTaO4涂层+1.5cm的纤维棉+8mm防火涂层+10mm纤维棉具有较好的隔热、抗氧化和防火性能。

Claims (6)

1.一种金属电池盒防火涂层的制备方法，其特征在于，包括以下步骤：
在金属电池盒外表面依次制备金属粘结层和稀土钽酸盐热障涂层；
在所述稀土钽酸盐热障涂层上包覆第一纤维棉层；其中，所述第一纤维棉层外表面涂有防火涂层；
采用粘结剂在所述防火涂层上包覆第二纤维棉层；
其中，所述防火涂层的制备方法为：
将氧化钙在去离子水中搅拌、分散均匀后得到固化剂；所述氧化钙和去离子水的质量比为1：（1~3），搅拌速率为100～600r/min，搅拌时间为30~90min；
称取稀土钽酸盐、氧化锆、二氧化硅、二氧化钛、氢氧化铝、玻璃粉和粘结剂，在搅拌机中搅拌均匀后与所述固化剂混合，再次搅拌均匀后，将其涂在所述第一纤维棉层上；所述稀土钽酸盐、氧化锆、二氧化硅、二氧化钛、氢氧化铝、玻璃粉和粘结剂的质量比为（1~3）：（1~2）：（1~2）：（1~2）：（1~2）：（1~2）：（3~6），搅拌速率为100～600r/min，搅拌时间为60~120min；
所述粘结剂为水玻璃。
2.如权利要求1所述的一种金属电池盒防火涂层的制备方法，其特征在于，采用超音速火焰喷涂方法在金属电池盒外表面制备所述金属粘结层；
所述金属粘结层的成分为NiCrAlY或CoCrAlY或NiCoCrAlY，球形率>97%，流动性为20~60s/50g，厚度为40~80µm；
所述超音速火焰喷涂方法的参数为：
所述金属电池盒的外表面温度为150~200℃，x轴喷枪枪速50~600mm/s，y轴喷枪枪速50~450mm/s，喷枪步距为5~12mm，喷枪枪距为0~360mm，燃烧室压力为0~160Pa，送粉速度为4~10rpm，氧气流量为500~1800scfh，载气流量为0~25scfh，进水温度为0~30℃，回水温度不高于50℃。
3.如权利要求1所述的一种金属电池盒防火涂层的制备方法，其特征在于，稀土钽酸盐热障涂层以YTaO4为原料，采用大气等离子喷涂方法制备；
所述YTaO4的球形率>97%，流动性为20~45s/50g，其在900℃的热导率为1.1~1.4Wm-1k-1；
所述稀土钽酸盐热障涂层厚度为100~150µm；
所述大气等离子喷涂方法的参数为：
所述金属电池盒的外表面温度为150~250℃，x轴喷枪枪速为1000~1800mm/s，y轴喷枪枪速为200~400mm/s，喷枪步距为5~10mm，喷枪枪距为100~220mm，系统电压为200~260V，电流为300~550A，功率为70~150W，送粉速度为5~8rpm，氩气流量为100~200scfh，氢气流量为20~60scfh，氮气流量为60~210scfh，载气流量为0~40scfh。
4.如权利要求3所述的一种金属电池盒防火涂层的制备方法，其特征在于，参与混合的所述固化剂占防火涂层材料总质量的1~3%，且混合时搅拌速率为100～600r/min，搅拌时间为60~120min；
所述防火涂层的厚度为5~15mm，常温下固化20~120h。
5.一种金属电池盒，其特征在于，其外表面具有防火涂层，所述防火涂层采用权利要求1-4任一所述的一种金属电池盒防火涂层的制备方法制成；
所述电池盒上设置有导热铜条，所述导热铜条一部分位于所述金属电池盒的内部空间，另一部分依次穿过金属电池盒和所述防火涂层后位于所述金属电池盒的外部空间。
6.如权利要求5所述的一种金属电池盒，其特征在于，还包括风冷装置，所述风冷装置朝向位于所述外部空间的所述导热铜条。
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