WO2017125041A1 - 电池芯内部用保护装置 - Google Patents

电池芯内部用保护装置 Download PDF

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Publication number
WO2017125041A1
WO2017125041A1 PCT/CN2017/071682 CN2017071682W WO2017125041A1 WO 2017125041 A1 WO2017125041 A1 WO 2017125041A1 CN 2017071682 W CN2017071682 W CN 2017071682W WO 2017125041 A1 WO2017125041 A1 WO 2017125041A1
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WIPO (PCT)
Prior art keywords
protection device
battery cell
battery
cell internal
electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/071682
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English (en)
French (fr)
Inventor
田雨
胡成
维尔纳⋅J.
山冈俊和
傅英松
陈建华
蔡⋅萊斯特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Littelfuse Electronics Shanghai Co Ltd
Tyco Electronics Japan GK
TE Connectivity Corp
Original Assignee
Raychem Electronics Shanghai Ltd
Tyco Electronics Japan GK
Tyco Electronics Corp
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Application filed by Raychem Electronics Shanghai Ltd, Tyco Electronics Japan GK, Tyco Electronics Corp filed Critical Raychem Electronics Shanghai Ltd
Publication of WO2017125041A1 publication Critical patent/WO2017125041A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/574—Devices or arrangements for the interruption of current
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • 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

  • the present disclosure relates to the field of battery technology, and more particularly to battery failure protection devices.
  • Batteries such as lithium battery packs, are very sensitive to faults caused by external short circuits, loss of charge control, and abuse of overcharge.
  • protective devices In order to provide overheating or overcurrent protection of the cell, protective devices have been developed.
  • the ideal battery protection device should be located inside the cell to ensure direct sensing of battery parameters, including current, electrolyte state temperature, and more.
  • the protection device is generally mounted outside the battery core.
  • the present disclosure proposes a protection device that can be used inside the battery core, which can avoid damage to the performance of the protection device by the internal environment of the battery core, thereby achieving safe and reliable protection inside the battery core.
  • a battery cell internal protection device including: a protection device for battery failure protection; two conductive terminals connected in series with the protection device at both ends of the protection device, The two conductive terminals respectively have a protection device joint, an electrode joint and a connection therebetween; and a seal covering the protection device joint of the protection device and the conductive terminal, and optionally covering either A portion of the connection portion of the conductive terminal.
  • the sealing device is used to tightly seal the protection device, thereby preventing the protection device from being affected by the internal environment of the battery core (such as electrolyte), thereby ensuring safe and reliable protection inside the battery core.
  • FIG. 1 is a schematic structural view of a protective device for a battery core according to an embodiment of the present disclosure, wherein the corrosion-resistant seal is indicated by a broken line.
  • Fig. 2 is a schematic side view of the protective device for the inside of the battery core shown in Fig. 1.
  • FIG 3 is a schematic side view showing a protective device for a battery core having a multilayer coating film seal according to an embodiment of the present disclosure.
  • FIG. 4 is a partial schematic view of a battery including a protection device for a battery core inside, in accordance with an embodiment of the present disclosure.
  • RT resistance temperature
  • FIG. 6 is a graph showing a result of a thermal shutdown test of a protective device for a battery core according to an embodiment of the present disclosure.
  • FIG. 7 is a graph showing test results of corrosion resistance of a sealing material according to an embodiment of the present disclosure.
  • the battery cell internal protection device of the present disclosure includes a protection device for battery failure protection, two conductive terminals for connecting the protection device and the electrode, and a seal for sealing the protection device.
  • 1 is a schematic structural view of a protective device for a battery core according to an embodiment of the present disclosure
  • FIG. 2 is a schematic side view of the protective device for a battery core shown in FIG. 1.
  • the battery core internal protection device includes a protection device 1, two conductive terminals 2, 2' and a sealing member 3. A detailed description of each component is as follows.
  • the protection device is the main component to achieve battery failure protection.
  • the protection device may comprise a resettable thermal cut off (TCO) device, a thermal fuse or a positive temperature coefficient (PTC) circuit protection device.
  • a positive temperature coefficient (PTC) circuit protection device may be a polymer positive temperature coefficient (PPTC) circuit protection device.
  • the battery cell internal protection device of the present disclosure can achieve multiple, repeated protection.
  • the protective device can take any shape suitable for use inside the battery. According to certain embodiments, the protective device can be in the form of a strip. According to some embodiments, the protection device can be chip shaped.
  • the strip protection device may have a size of 1 mm to 5 mm in width, 0.5 mm to 2 mm in thickness, and no limitation in length.
  • a conductive terminal is used to connect the protection device and the electrode, wherein one conductive terminal is used to connect the protection device to the internal electrode of the battery cell, and the other conductive terminal is used to connect the protection device to the battery
  • the cap of the core is in turn connected to the external electrode for a serial connection.
  • two conductive terminals are connected in series with the protection device at both ends of the protection device, the two conductive terminals respectively having a protection device junction, an electrode bond, and between Connection.
  • the conductive terminal 2 includes a protective device bonding portion 21 for bonding to the protective device 1, an electrode bonding portion 23 for bonding to the electrode, and a connecting portion 22 therebetween.
  • the conductive terminal 2' includes a protective device bonding portion 21' for bonding to the protective device 1, an electrode bonding portion 23' for bonding to the electrode, and a connecting portion 22' therebetween. Note that since the two conductive terminals are located differently from the electrodes used for the connection, The specific shape and structure of their respective protective device joints, electrode joints and joints may vary.
  • the conductive terminals 2 and 2' are respectively in the form of a sheet.
  • the conductive terminal 2 (lower conductive terminal) is connected to the lower surface of the protective device 1, and the protective device bonding portion 21, the electrode bonding portion 23, and the connecting portion 22 are substantially in the same plane.
  • the conductive terminal 2' (upper conductive terminal) is attached to the upper surface of the protective device 1, and the connecting portion 22' is curved so that the electrode joint portion 23' is substantially at the same level as the conductive terminal 2.
  • the conductive terminals 2' may take other configurations, for example, the protective device bonding portion 21', the electrode bonding portion 23', and the connecting portion 22' may also be substantially in the same plane.
  • the bonding of the protective device joints 21 and 21' of the conductive terminals 2 and 2' to the protective device 1 may be any suitable combination, such as riveting, soldering (including spot welding, laser welding, etc.), depending on the specific application and purpose. .
  • the protective device bond of the conductive terminal may cover the entire surface of the protection device or may cover a portion of the surface of the protection device.
  • the protection device is a PTC (especially PPTC) circuit protection device having a large coefficient of thermal expansion
  • the manner of bonding the surface of the cover portion is preferred so that the protection device has sufficient free thermal expansion space.
  • the electrode joints 23 and 23' of the conductive terminals 2 and 2' may be used to be respectively connected to the internal electrodes and the cap of the battery cell by riveting, soldering or the like.
  • the electrode joint portion 23 of the conductive terminal 2 (lower conductive terminal) has a structure for riveting
  • the electrode joint portion 23' of the conductive terminal 2' is used for soldering. Connected to the electrode.
  • the connection manner of the two electrode joint portions may be reversed from the above, or the connection manner of the two may be the same.
  • the material of the conductive terminal of the present disclosure is not particularly limited, and a conductive terminal material commonly used in the art, such as a metal such as nickel, copper, tin-plated copper, stainless steel or copper-plated stainless steel, or the like can be used.
  • a conductive terminal material commonly used in the art such as a metal such as nickel, copper, tin-plated copper, stainless steel or copper-plated stainless steel, or the like can be used.
  • the thickness of the sheet-shaped conductive terminals is usually from 0.05 mm to 0.5 mm.
  • a sheet-shaped conductive terminal having a thickness of 0.05 mm or more can ensure a certain strength.
  • the electrode joint of the conductive terminal can take a folded design, as shown in Figures 1 and 2.
  • the folded design of the electrode joint enhances the strength of the terminal and ensures the reliability of riveting or soldering the assembly with the electrode.
  • the connection portion of the conductive terminal between the protection device joint portion and the electrode joint portion is relatively low in strength, providing relatively good flexibility and ensuring the protector The piece expands freely and enhances the reliability of the protection device inside the battery core.
  • the sealing member is used for sealing the protection device to ensure protection of the device from corrosion from the internal environment of the battery core, wherein the protection device is invaded in the electrolyte of the lithium battery cell, and the main components include :lithium (lithium) Hexafluorophosphate (hexafluorophosphate), Ethylene Carbonate (ethylene carbonate), Ethyl Methyl Carbonate (ethyl methyl carbonate), diethyl carbonate (diethyl carbonate).
  • the seal covers the entire protective device and may cover a portion of the connection of any one of the conductive terminals.
  • the sealing member 3 completely covers the protective device 1, including the protective device bonding portions 21 and 21' in which the conductive terminals are combined with the protective device, and the sealing member 3 also extends outwardly a distance, that is, a connection covering the conductive terminals. Part of sections 22 and 22'.
  • the sealing performance of the protective device is enhanced by covering the seal over a sufficient distance beyond the protective device.
  • the seal is flexible.
  • the flexible seal can conform to the thermal expansion or contraction of the protective device to ensure a sealed effect on the protective device.
  • the seal comprises at least one of a heat shrink sleeve, an injection molding, and a coating film.
  • the material of the heat shrinkable sleeve is mainly plastic, including PVC (polyvinyl chloride), PP (polypropylene) EVA (ethylene-vinyl acetate copolymer), PET (polyethylene terephthalate), etc., through extrusion Forming a plastic sleeve of a given size and shape, and then irradiating the polymer to crosslink. The size of the sleeve is magnified by the mold.
  • the heat shrink tubing can be a double heat shrink tubing.
  • a better sealing effect can be achieved for the protective device.
  • the outer layer of the double-layer heat-shrinkable sleeve is semi-hard PP, which provides sufficient strength and the inner material is soft PP. To ensure a better seal.
  • the seal can be formed by an injection molding or coating process.
  • the material used for injection molding may be a plastic material having corrosion resistance, including LCP (liquid crystal) Polymer), PBS (polybutylene succinate), PE (polyethylene), PC (polycarbonate), and the like.
  • the material used in the coating process may be a curable material having corrosion resistance, including certain thermosetting resins such as epoxy resin, polyurethane, acrylic resin, silicone resin, parylene, fluororesin. Wait.
  • the coating film formed by the coating process may have a multilayer structure.
  • 3 is a side cross-sectional view showing a protective device for a battery core having a multilayer structure layered sealing member according to an embodiment of the present disclosure.
  • the layered sealing member includes a flexible adhesive coating 31, an oxygen barrier layer 32, and a corrosion resistant coating 33 in this order from the inside to the outside.
  • the use of a layered sealing element with a multi-layer coating significantly improves the protection of the protective device.
  • the main component of the flexible adhesive coating 31 is silicone, which not only ensures the bonding force of the layered sealing member and the protective device, but also provides a cushioning effect to reduce the generation of internal stress.
  • the main component of the oxygen barrier layer 32 is epoxy resin, which protects the device from oxidizing factors such as oxygen.
  • the outermost anti-corrosion coating 33 is mainly composed of a fluororesin to provide protection against the electrolyte inside the cell.
  • the multilayer coating is not limited to the three-layer structure shown in Fig. 3, and an appropriate number of layers (e.g., two layers) and functions of the respective layers can be selected as needed.
  • a heat shrinkable sleeve when used as the seal, it can also be provided at the boundary between the heat shrinkable sleeve boundary (ie, the portion covered with the heat shrinkable sleeve and the portion not covered with the heat shrinkable sleeve).
  • One or more layers of corrosion resistant sealing layer The material of the anti-corrosion sealing layer may be the same as that of the above-mentioned injection molded part or coating film. The sealing effect of the seal is further improved by sealing the possible open area of the heat shrinkable sleeve with an anti-corrosive sealing layer.
  • the thickness of the seal can be from 0.02 mm to 1 mm. According to certain embodiments, the thickness of the seal may be 0.1 mm or more, or 0.2 mm or more, and 0.5 mm or less, or 0.6 mm or less. A thickness of 0.02 mm or more can ensure the sealing strength of the sealing member, and a thickness of not more than 1 mm can avoid the problem of increasing the overall thickness of the protective device inside the battery core, thereby facilitating the use inside the battery core.
  • the battery cell internal protection device of the present disclosure can be manufactured by the following method.
  • the method includes: providing a protection device for battery failure protection; respectively bonding two conductive terminals to the two ends of the protection device to form a serial connection, the two conductive terminals respectively having a protection device combination a portion, an electrode joint, and a connection therebetween; and applying a seal to the protective device, the seal covering the protective device joint of the protective device and the conductive terminal, and optionally covering any one of the conductive terminals Part of the connection.
  • the manner in which the protective device bond of the conductive terminal and the protective device are combined includes riveting or soldering.
  • the manner in which the seal is applied to the protective device includes a heat shrink sleeve process, an injection molding process, or a coating process.
  • the coating process can be performed multiple times to form a multilayer coating.
  • the method of making a protective device for a battery core interior further includes the step of sealing the heat shrinkable sleeve boundary with a corrosion resistant sealing layer.
  • the conductive terminal and the sealing member refer to the section "Protective device for internal battery core" described above.
  • the present disclosure also relates to a battery including the above-described protective device for the inside of the battery core.
  • one of the two conductive terminals of the battery core internal protection device is connected to the internal electrode of the battery cell, and the other end of the battery cell is connected to the external electrode to protect the internal battery core.
  • the device is assembled inside the battery core and is connected in series with one electrode of the battery core.
  • FIG. 4 is a partial structural schematic view of a typical battery including a protective device for a battery cell inside of the present disclosure, wherein the circuit protection device 100 is fixed to the cap 300 of the battery cell by an insulating material 200, and the external positive electrode connecting portion 400 of the battery cell passes
  • the riveting is connected to one of the conductive terminals of the circuit protection device 100 through the insulating material 200, and the other conductive terminal of the circuit protection device 100 is connected to the conductive strip 500 by spot welding, thereby being connected to the positive electrode film inside the battery core, thereby realizing the positive electrode. connection.
  • the conductive tape 500 is directly connected to the negative electrode film and the cap 300 inside the battery core, thereby achieving a negative electrode connection.
  • the tested product adopts the structure shown in Fig. 1.
  • the protection device is a polymer positive temperature coefficient (PPTC) circuit protection device.
  • the conductive terminal is a nickel strip with a thickness of 0.15 mm and a hardness of one-half.
  • the seal is double-layered. Heat shrink tubing.
  • the test product is immersed in a lithium battery electrolyte (main components include: lithium (Lithium) Hexafluorophosphate (hexafluorophosphate), Ethylene Carbonate (ethylene carbonate), Ethyl Methyl Carbonate (ethyl methyl carbonate), diethyl carbonate (diethyl carbonate) Ethyl ester)), refer to IEC6008-2-14 measurement method N: temperature change, put into the temperature impact furnace (model: Jufu ETST-056-65-AW) for temperature impact test, test conditions: -40 ° C ⁇ At 85 ° C, each temperature cycle lasts for 2 hours (the test sample has a conversion time of less than 30 seconds per temperature cycle conversion), 20 cycles.
  • main components include: lithium (Lithium) Hexafluorophosphate (hexafluorophosphate), Ethylene Carbonate (ethylene carbonate), Ethyl Methyl Carbonate (ethyl methyl carbonate), diethyl carbonate
  • the battery protection device is capable of thermal shutdown (Thermal Cut Off) to provide timely protection when the battery core is heated to the extreme temperature.
  • the tested products were tested for thermal shutdown as follows: The sample tested passed a current of 1 A and placed in an incubator to simulate the heating of the cell. The temperature rise rate of the incubator was set to 1 degree/min, and the resistance of the circuit protection device was recorded. The change in temperature and the temperature at which the resistance is abrupt are recorded as the thermal shutdown temperature.
  • the circuit protection device performs three thermal shutdown simulation experiments.
  • the test results refer to Figure 6.
  • the three test results show that the thermal shutdown temperature is consistent.
  • the method for evaluating the corrosion resistance of the sealing material is as follows.
  • the sealing material is immersed in the electrolyte (the main components include: lithium (Lithium) Hexafluorophosphate (hexafluorophosphate), Ethylene Carbonate (ethylene carbonate), Ethyl Methyl Carbonate (Ethyl Methyl Carbonate) Ethyl methyl carbonate), diethyl carbonate (diethyl carbonate), stored at room temperature and 60 ° for a certain period of time, measurement
  • the change in weight of the sealing material is used to evaluate the resistance of the raw material to electrolyte corrosion.
  • the test results of the selected heat shrinkable sleeve are shown in Figure 7.
  • the test results show that the heat shrinkable sleeve test at room temperature has a weight loss of 4.92% per day, a weight loss of 4.39% per week, a weight loss of 4.2% for 2 weeks, and a weight loss of one day at 60 degrees. 1.4%, a one-week weight loss of 1.49%, and a 2-week weight loss of 1.56%.
  • the test results of the electrolyte corrosion resistance of the heat shrinkable sleeve show that the performance of the heat shrinkable sleeve is affected by the electrolyte, but the weight loss after one day of testing does not change significantly with time, and the corrosion resistance of the electrolyte becomes stable.
  • the corrosion resistance test results of the combined product show that the long-term electrolyte use environment can maintain the product performance is relatively stable.
  • the battery cell internal protection device of the present disclosure and the battery using the same may have at least one of the following advantages:
  • the protection device inside the battery core can realize multiple times and repeated protection.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Connection Of Batteries Or Terminals (AREA)

Abstract

本公开涉及电池芯内部用保护装置。本公开的电池芯内部用保护装置包括：用于电池失效保护的保护器件；在所述保护器件两端、与所述保护器件串行连接的两个导电端子，所述两个导电端子分别具有保护器件结合部、电极结合部和位于两者之间的连接部；和密封件，所述密封件覆盖保护器件和导电端子的保护器件结合部，并且任选覆盖任一个导电端子的连接部的一部分。该电池芯内部用保护装置可以避免电池芯内部环境对电池失效保护器件性能的损伤，在电池芯内部实现安全可靠的保护。

Description

电池芯内部用保护装置 技术领域
本公开涉及电池技术领域，尤其涉及电池失效保护装置。
背景技术
蓄电池，例如锂电池组，对于外部短路、充电失控和滥用过充等引起的故障非常敏感。为了提供电池芯过热或过流保护，已经开发出了保护器件。理想的电池保护器件应该位于电池芯内部以确保直接感应电池参数，包括电流、电解质状态温度等。但是，由于没有解决电池芯内部环境对保护器件性能的损伤问题，保护器件一般安装在电池芯外部。
发明内容
本公开提出了一种可以用于电池芯内部的保护装置，其可以避免电池芯内部环境对保护器件性能的损伤，从而在电池芯内部实现安全可靠的保护。
本公开的一个方面涉及一种电池芯内部用保护装置，包括：用于电池失效保护的保护器件；在所述保护器件两端、与所述保护器件串行连接的两个导电端子，所述两个导电端子分别具有保护器件结合部、电极结合部和位于两者之间的连接部；和密封件，所述密封件覆盖保护器件和导电端子的保护器件结合部，并且任选覆盖任一个导电端子的连接部的一部分。
在本公开中，采用密封件对保护器件进行严格密封，避免了保护器件受到电池芯内部环境(例如电解质)的影响，从而保证在电池芯内部实现安全可靠的保护。
附图说明
图1是根据本公开一个实施方案的电池芯内部用保护装置的结构示意图，其中耐腐蚀密封件用虚线表示。
图2是图1所示的电池芯内部用保护装置的示意性侧视图。
图3是显示根据本公开一个实施方案的具有多层涂膜密封的电池芯内部用保护装置的示意性侧视图。
图4是根据本公开一个实施方案的包括电池芯内部用保护装置的电池的局部示意图。
图5是根据本公开一个实施方案的电池芯内部用保护装置在电解液模拟测试前后的电阻温度(RT)曲线图。
图6是显示根据本公开一个实施方案的电池芯内部用保护装置的热关断测试结果的曲线图。
图7是显示根据本公开一个实施方案的密封材料耐腐蚀性能测试结果的曲线图。
具体实施方式
下面对本公开提供的电池芯内部用保护装置、其制造方法和使用该电池芯内部用保护装置的电池的一些具体实施方式进行描述。
应当理解，在不脱离本发明的范围或精神的情况下，本领域技术人员能够根据本公开的教导设想其他各种实施方案并能够对其进行修改。因此，以下的具体实施方式不具有限制性意义。
除非另外指明，否则说明书和权利要求中使用的表示特征尺寸、数量和物理特性的所有数字均应该理解为在所有情况下均是由术语“约”来修饰的。因此，除非有相反的说明，否则说明书和所附权利要求书中列出的数值参数均是近似值，本领域的技术人员能够利用本文所公开的教导内容寻求获得的所需特性，适当改变这些近似值。用端点表示的数值范围的使用包括该范围内的所有数字以及该范围内的任何范围，例如，1至5包括1、1.1、1.3、1.5、2、2.75、3、3.80、4和5等等。
1.电池芯内部用保护装置
本公开的电池芯内部用保护装置包括用于电池失效保护的保护器件、用于连接保护器件和电极的两个导电端子和用于密封保护器件的密封件。图1示出了根据本公开一个实施方案的电池芯内部用保护装置的结构示意图，图2是图1所示的电池芯内部用保护装置的示意性侧视图。如图1和 2所示，电池芯内部用保护装置包括保护器件1、两个导电端子2、2’和密封件3。各个部件的详细描述如下。
保护器件：
保护器件是实现电池失效保护的主要部件。根据某些具体实施方案，保护器件可以包括可复位热关断(thermal cut off,TCO)器件、温度保险丝(thermal fuse)或正温度系数(Positive Temperature Coefficient,PTC)电路保护器件。根据某些具体实施方案，正温度系数(Positive Temperature Coefficient,PTC)电路保护器件可以是聚合物正温度系数(Polymer Positive Temperature Coefficient,PPTC)电路保护器件。
当采用TCO或PTC电路保护器件时，本公开的电池芯内部用保护装置可以实现多次、重复保护。
保护器件可以采取适用于在电池内部使用的任何形状。根据某些具体实施方案，保护器件可以为带状设计。根据某些具体实施方案，保护器件可以是芯片状的。
根据某些具体实施方案，带状保护器件的尺寸：宽度可以为1mm～5mm，厚度可以为0.5mm～2mm，长度不加以限制。
导电端子
本公开的电池芯内部用保护装置中，导电端子用于连接保护器件和电极，其中一个导电端子用于将保护器件连接至电池芯的内部电极，另一个导电端子用于将保护器件连接至电池芯的盖帽进而连接到外部电极，实现串行连接。
根据某些具体实施方案，两个导电端子在所述保护器件两端，与所述保护器件串行连接，所述两个导电端子分别具有保护器件结合部、电极结合部和位于两者之间的连接部。如图1所示，导电端子2包括用于结合于保护器件1的保护器件结合部21、用于结合于电极的电极结合部23和位于两者之间的连接部22。同样，导电端子2’包括用于结合于保护器件1的保护器件结合部21’、用于结合于电极的电极结合部23’和位于两者之间的连接部22’。注意，由于两个导电端子所处位置和用于连接的电极不同， 它们各自的保护器件结合部、电极结合部和连接部的具体形状和结构可以不同。
在图1所示的结构中，导电端子2和2’分别为片状。导电端子2(下导电端子)连接于保护器件1的下表面，其保护器件结合部21、电极结合部23和连接部22基本上处于同一平面。导电端子2’(上导电端子)连接于保护器件1的上表面，其连接部22’是弯曲的，以使得电极结合部23’与导电端子2基本上处于同一水平。当然，导电端子2’也可以采取其他结构，例如保护器件结合部21’、电极结合部23’和连接部22’也可以基本上处于同一平面。
导电端子2和2’的保护器件结合部21和21’与保护器件1的结合可以是任何合适的结合方式，例如铆接、焊接(包括点焊、激光焊等)，根据具体应用和目的而定。对于带状或片状保护器件而言，导电端子的保护器件结合部可以覆盖保护器件的整个表面，也可以覆盖保护器件的部分表面。当保护器件是具有大的热膨胀系数的PTC(尤其是PPTC)电路保护器件时，覆盖部分表面的结合方式是优选的，以使保护器件具有足够的自由热膨胀空间。
导电端子2和2’的电极结合部23和23’可以用于以铆接、焊接等方式分别连接至电池芯的内部电极和盖帽上。在图1所示的结构示意图中，导电端子2(下导电端子)的电极结合部23具有用于铆接的结构，导电端子2’(上导电端子)的电极结合部23’用于通过焊接方式连接于电极。但是，两个电极结合部的连接方式也可以与上述相反，或者两者的连接方式也可以相同。
本公开对导电端子的材料没有特别限制，可以采用本领域中常用的导电端子材料，例如金属，如镍、铜、镀锡的铜、不锈钢或镀铜的不锈钢等。当导电端子为片状时，片状导电端子的厚度通常为0.05mm-0.5mm。厚度为0.05mm以上的片状导电端子可以确保一定的强度。
根据某些具体实施方案，导电端子的电极结合部可以采取折叠设计，如图1和图2所示。电极结合部的折叠设计可以增强端子的强度，确保与电极铆接或焊接装配的可靠性。而导电端子的位于保护器件结合部和电极结合部之间的连接部强度相对较低，提供比较好的柔性，可以确保保护器 件自由膨胀，增强电池芯内部用保护装置的可靠性。
密封件
本公开的电池芯内部用保护装置中，密封件用于密封保护器件，确保保护器件免受来自电池芯内部环境的腐蚀影响，其中保护器件侵泡于锂电池芯的电解液中，主要成分包括：lithium(锂)Hexafluorophosphate(六氟磷酸盐)，Ethylene Carbonate(碳酸亚乙酯)，Ethyl Methyl Carbonate(碳酸甲乙酯)，diethyl carbonate(碳酸二乙酯)。
根据某些具体实施方案，密封件覆盖整个保护器件，并且可以覆盖任一个导电端子的连接部的一部分。如图1所示，密封件3完全覆盖保护器件1，包括导电端子与保护器件结合的保护器件结合部21和21’，而且密封件3还向外延伸一段距离，即，覆盖导电端子的连接部22和22’的一部分。通过使密封件覆盖超过保护器件足够的距离，增强了对保护器件的密封性能。
根据某些具体实施方案，密封件是柔性的。柔性密封件可以顺从保护器件的热膨胀或收缩，确保对保护器件的密封效果。
根据某些具体实施方案，密封件包括热缩套管、注塑成型和涂膜中的至少一种。
热缩套管的材料主要是塑料，包括PVC(聚氯乙烯)，PP(聚丙烯)EVA(乙烯-醋酸乙烯共聚物)，PET(聚对苯二甲酸乙二酯)等等，通过挤出成型为既定尺寸和形状的塑料套管，然后采用辐照技术使聚合物产生交联，套管的尺寸通过模具放大，在受热的状况下，辐照产生的聚合物交联促使套管收缩到既定的尺寸和形状，从而为其保护的部件提供绝缘密封，进而确保热缩套管密封的部件具有隔离外部环境影响提供功能。根据某些具体实施方案，热缩套管可以是双层热缩套管。在采用双层热缩套管的情况下，可以实现对保护器件的更佳密封效果，双层热缩套管外层材料为半硬的PP，提供足够的强度，内部材料为软的PP，以确保具有更好的密封性。
密封件可以通过注塑成型或涂覆工艺形成。根据某些具体实施方案，用于注塑成型的材料可以是具有耐腐蚀性的塑性材料，包括LCP(液晶 聚合物)、PBS(聚丁二酸丁二醇酯)、PE(聚乙烯)、PC(聚碳酸脂)等。根据某些具体实施方案，用于涂覆工艺的材料可以是具有耐腐蚀性的固化性材料，包括某些热固性树脂，如环氧树脂、聚氨酯、丙烯酸树脂、硅树脂、派瑞林、氟树脂等。
在某些具体实施方案中，通过涂覆工艺形成的涂膜可以具有多层结构。图3示出了根据本公开一个实施方案的具有多层结构层状密封元件的电池芯内部用保护装置的侧面剖视图。图3中，层状密封元件由内向外依次包括柔性粘合剂涂层31、阻氧层32和抗腐蚀涂层33。采用具有多层涂层的层状密封元件，显著提高了对保护器件的保护效果。例如，柔性粘合剂涂层31的主要成分为硅树脂，不仅保证层状密封元件与保护器件的结合力，而且还可提供缓冲作用，减少内部应力的产生。阻氧层32主要成份是环氧树脂，能够保护保护器件免受氧气等氧化性因素的影响。最外层的抗腐蚀涂层33主要成份是氟树脂，提供对电池芯内部电解质的防护作用。多层涂层不限于图3所示的三层结构，可以根据需要选择适当的层数(例如双层)和各个层的功能。
需要指出的是，在采用热缩套管作为密封件时，还可以在热缩套管边界(即覆盖有热缩套管的部分和未覆盖有热缩套管的部分之间的界面)提供一层或多层的抗腐蚀密封层。抗腐蚀密封层的材料可以与上述的注塑成型件或涂膜的材料相同。通过用抗腐蚀密封层密封热缩套管的可能的开口区域，进一步提高了密封件的密封效果。
密封件的厚度可以为0.02mm至1mm。根据某些具体实施方案，密封件的厚度可以为0.1mm以上，或0.2mm以上，并且为0.5mm以下，或0.6mm以下。0.02mm以上的厚度可以保证密封件的密封强度，而不超过1mm的厚度可以避免增加电池芯内部用保护装的整体厚度的问题，从而利于在电池芯内部使用。
2.制造电池芯内部用保护装置的方法
本公开的电池芯内部用保护装置可以通过以下方法制造。所述方法包括：提供用于电池失效保护的保护器件；将两个导电端子分别结合至所述保护器件两端，形成串行连接，所述两个导电端子分别具有保护器件结合 部、电极结合部和位于两者之间的连接部；和将密封件施加于保护器件上，所述密封件覆盖保护器件和导电端子的保护器件结合部，并且任选覆盖任一个导电端子的连接部的一部分。
根据某些具体实施方案，导电端子的保护器件结合部与保护器件的结合方式包括铆接或焊接。
根据某些具体实施方案，密封件在保护器件上的施加方式包括热缩套管工艺、注塑成型或涂覆工艺。
根据某些具体实施方案，涂覆工艺可以进行多次，以形成多层涂层。
根据某些具体实施方案，制造电池芯内部用保护装置的方法还包括将热缩套管边界用抗腐蚀密封层密封的步骤。
关于保护器件、导电端子和密封件的结构和材料，参见上述的“电池芯内部用保护装置”部分。
3.包括电池芯内部用保护装置的电池
本公开还涉及包括上述电池芯内部用保护装置的电池。根据某些具体实施方案，电池芯内部用保护装置的两个导电端子中的一个连接至电池芯的内部电极，另一个连接至电池芯的盖帽用于连接外接电极，从而将电池芯内部用保护装置装配到电池芯内部，同电池芯的一个电极实现串行连接。
图4显示了本公开的一个典型的包括电池芯内部用保护装置的电池的局部结构示意图，其中电路保护装置100通过绝缘材料200固定到电池芯的盖帽300上，电池芯外部正极连接部分400通过铆接，穿过绝缘材料200同电路保护装置100的一个导电端子连接固定，而电路保护装置100的另一个导电端子通过点焊同导电带500连接，进而连接到电池芯内部正极薄膜，从而实现正极连接。导电带500直接同电池芯内部负极薄膜和盖帽300连接，从而实现负极连接。采用此简单构造，电路保护装置100铆接的电池芯外部正极连接部分400和盖帽300上点焊连接的电池芯外部负极连接部分600分别作为连接接口成为电池芯的正极和负极输出。
4.性能测试
(1)耐腐蚀性能测试
测试的产品采用图1所示的结构，其中保护器件是聚合物正温度系数(PPTC)电路保护器件，导电端子采用厚度0.15mm，硬度为二分之一硬的镍带，密封件为双层的热缩套管。
将测试的产品浸入锂电池电解液(主要成分包括：lithium(锂)Hexafluorophosphate(六氟磷酸盐)，Ethylene Carbonate(碳酸亚乙酯)，Ethyl Methyl Carbonate(碳酸甲乙酯)，diethyl carbonate(碳酸二乙酯))中，参考IEC6008-2-14测量方法N：温度变化，放到温度冲击炉中(型号：巨孚ETST-056-65-AW)做温度冲击试验，测试条件：-40℃～85℃,每个温度循环持续时间2小时(测试的样品在每个温度循环转换的转换时间小于30秒)，20个循环。
测试前后对比电路保护器件的电阻温度特性参见附图5，从结果上看，测试前后电路保护器件电阻温度特性保持一致，电路保护器件的性能没有受到电池电解液的腐蚀影响，增加了密封件可以有效的保护电路保护器件受电解液的腐蚀影响，电路保护产品的性能得以保护。
(2)重复使用性能
采用与“耐腐蚀性能测试”中结构相同的产品进行重复使用性能测试。
过冲情况下，电池芯发热，需要电池芯发热到极限温度时，电路保护装置能够进行热关断(Thermal Cut Off)以提供及时保护。测试的产品热关断的测试如下：测试的样品通过1A的电流，置于温箱中用于模拟电池芯发热，温箱的温度上升速度设置为1度/分钟，记录电路保护装置的电阻随温度的变化，电阻突变时的温度记录为热关断温度。
电路保护装置进行3次热关断模拟实验，测试结果参照附图6，三次测试结果显示热关断温度一致性较好。
(3)密封材料的耐腐蚀性测试
密封材料的耐电解液腐蚀性能评估方法如下，将密封材料浸入到电解液中(主要成分包括：lithium(锂)Hexafluorophosphate(六氟磷酸盐)，Ethylene Carbonate(碳酸亚乙酯)，Ethyl Methyl Carbonate(碳酸甲乙酯)，diethyl carbonate(碳酸二乙酯))，在室温和60度下保存一定时间，测量 密封材料的重量变化来评估原材料的耐电解液腐蚀能力。选择的热缩套管测试结果见附图7，测试结果显示：室温下热缩套管测试一天重量损失4.92％，一周重量损失4.39％，2周重量损失4.2％，60度下测试一天重量损失1.4％，一周重量损失1.49％，2周的重量损失为1.56％。热缩套管的耐电解液腐蚀性能测试结果显示，热缩套管性能会受到电解液的影响，但是一天测试后的重量损失随着时间没有明显改变，耐电解液腐蚀性能会变的稳定，结合产品的耐腐蚀性能测试结果说明长期的电解液使用环境下可以保持产品性能相对稳定。
根据上述具体实施方案，本公开的电池芯内部用保护装置和使用其的电池可以具有以下优点中的至少一项：
(1)实现了电池失效保护的电池芯内部化，避免了避免电池芯内部环境对电池失效保护器件性能的影响；
(2)可以直接感应电池参数如电流、电解质状态温度等的变化，使得电池失效保护更加可靠安全；
(3)在采用TCO或PTC电路保护器件时，电池芯内部用保护装置可以实现多次、重复保护。
应当理解，上述具体实施方案仅是为了说明本发明，而非限制本发明的范围。本领域技术人员可以在不脱离本发明的精神的前提下进行各种修改和变更。本发明的范围由后附的权利要求书限定。

Claims (12)

  1. 一种电池芯内部用保护装置，包括：
    用于电池失效保护的保护器件；
    在所述保护器件两端、与所述保护器件串行连接的两个导电端子，所述两个导电端子分别具有保护器件结合部、电极结合部和位于两者之间的连接部；和密封件，所述密封件覆盖保护器件和导电端子的保护器件结合部，并且任选覆盖任一个导电端子的连接部的一部分。
  2. 根据权利要求1所述的电池芯内部用保护装置，其中所述保护器件包括可复位热关断(TCO)器件、温度保险丝或正温度系数(PTC)电路保护器件。
  3. 根据权利要求2所述的电池芯内部用保护装置，其中所述正温度系数电路保护器件是聚合物正温度系数(PPTC)电路保护器件。
  4. 根据权利要求1所述的电池芯内部用保护装置，其中所述保护器件是芯片状的。
  5. 根据权利要求1所述的电池芯内部用保护装置，其中一个导电端子的电极结合部用于结合电池芯的内部电极，另一个导电端子的电极结合部用于结合电池芯的盖帽进而连接到外接电极。
  6. 根据权利要求1所述的电池芯内部用保护装置，其中所述导电端子是片状的。
  7. 根据权利要求6所述的电池芯内部用保护装置，其中至少一个导电端子的电极结合部具有折叠结构。
  8. 根据权利要求1所述的电池芯内部用保护装置，其中所述密封件包括热缩套管、注塑成型件和涂膜的至少一种。
  9. 根据权利要求8所述的电池芯内部用保护装置，其中所述热缩套管包括双层热缩套管。
  10. 根据权利要求8所述的电池芯内部用保护装置，其中所述涂膜具有多层结构。
  11. 根据权利要求8所述的电池芯内部用保护装置，还包括用于密封所述热缩套管边界的密封层。
  12. 根据权利要求1所述的电池芯内部用保护装置，所述电池芯内部用保护装置是带状的。
PCT/CN2017/071682 2016-01-20 2017-01-19 电池芯内部用保护装置 Ceased WO2017125041A1 (zh)

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