本申请属于电池领域，涉及一种电池和电子设备。The present application belongs to the field of batteries and relates to a battery and an electronic device.
随着新能源领域的迅猛发展，高能量密度和高安全性能是新能源领域对锂离子电池的迫切需求。相比于传统的液态电池，高比能电池具有能量密度高，续航力长等特点，在尖端消费电子产品、电动汽车、储能设备等新能源领域具有更为广阔的应用前景。With the rapid development of new energy, high energy density and high safety performance are the urgent needs of lithium-ion batteries in the new energy field. Compared with traditional liquid batteries, high specific energy batteries have the characteristics of high energy density and long endurance, and have broader application prospects in new energy fields such as cutting-edge consumer electronics, electric vehicles, and energy storage equipment.
半固态电池或固态电池是向高比能电池过渡的一种迭代产品，其与液态电池中同样含有正负极片和隔离膜，不同之处在于半固态电池中使用的是半固态电解质，固态电池使用的是固态电解质，液态电池中使用的是液态电解质。相比于液态电池，半固态电池或固态电池对热稳定性的需求更大，因此提高半固态或固态电池的安全性，是本领域持续关注的热点之一。Semi-solid batteries or solid-state batteries are an iterative product in the transition to high-energy-density batteries. They contain positive and negative electrodes and isolation membranes like liquid batteries. The difference is that semi-solid batteries use semi-solid electrolytes, solid-state batteries use solid electrolytes, and liquid batteries use liquid electrolytes. Compared with liquid batteries, semi-solid batteries or solid-state batteries have a greater demand for thermal stability. Therefore, improving the safety of semi-solid or solid-state batteries is one of the hot topics that continue to be concerned about in this field.
发明内容Summary of the invention
本申请提供一种电池，包括电解质，电解质具有较好的热稳定性，有助于延长电池的ARC热失控时间，提高电池的安全性。The present application provides a battery, including an electrolyte, wherein the electrolyte has good thermal stability, which helps to prolong the ARC thermal runaway time of the battery and improve the safety of the battery.
本申请还提供一种电子设备，包括上述电池。The present application also provides an electronic device, comprising the above-mentioned battery.
本申请提供一种电池，包括电解质；The present application provides a battery, comprising an electrolyte;
在氮气气氛下，以5℃/min的升温速度对所述电解质进行热重分析，所述电解质在100℃～600℃之间至少存在一个失重峰。In a nitrogen atmosphere, a thermogravimetric analysis is performed on the electrolyte at a heating rate of 5° C./min, and the electrolyte has at least one weight loss peak between 100° C. and 600° C.
如上所述的电池，所述电解质在100℃～600℃下的失重率为3～85％。In the battery as described above, the weight loss rate of the electrolyte at 100° C. to 600° C. is 3 to 85%.
如上所述的电池，在氮气气氛下，从初始温度T0开始，以5℃/min的升温速率对所述电解质进行热重分析，初始温度T0为25℃，初始温度T0下电解质的质量为M0；For the battery as described above, a thermogravimetric analysis of the electrolyte is performed under a nitrogen atmosphere, starting from an initial temperature T0 at a heating rate of 5° C./min, wherein the initial temperature T0 is 25° C., and the mass of the electrolyte at the initial temperature T0 is M0 ;
所述电解质满足下述至少一项：The electrolyte satisfies at least one of the following:
(1)当温度T到达100℃时，电解质的质量≥96.13％*M0；(1) When the temperature T reaches 100°C, the mass of the electrolyte is ≥96.13%*M0 ;
(2)当温度T到达200℃时，电解质的质量≥49.46％*M0；(2) When the temperature T reaches 200°C, the mass of the electrolyte is ≥49.46%*M0 ;
(3)当温度T到达300℃时，电解质的质量≥35.02％*M0；(3) When the temperature T reaches 300°C, the mass of the electrolyte is ≥35.02%*M0 ;
(4)当温度T到达400℃时，电解质的质量≥27.51％*M0；(4) When the temperature T reaches 400°C, the mass of the electrolyte is ≥ 27.51%*M0 ;
(5)当温度T到达500℃时，电解质的质量≥19.06％*M0；(5) When the temperature T reaches 500°C, the mass of the electrolyte is ≥19.06%*M0 ;
(6)当温度T到达590℃时，电解质的质量≥17.74％*M0。(6) When the temperature T reaches 590°C, the mass of the electrolyte is ≥17.74%*M0 .
如上所述的电池，所述电解质的X射线衍射图中具有M个2θ衍射角为x的第一衍射峰和N个2θ衍射角为y的第二衍射峰，M≥1，N≥1；The battery as described above, wherein the electrolyte has M first diffraction peaks with a 2θ diffraction angle of x and N second diffraction peaks with a 2θ diffraction angle of y in an X-ray diffraction pattern, M≥1, N≥1;
其中，10°≤x≤30°，30°≤y≤50°；Among them, 10°≤x≤30°, 30°≤y≤50°;
M个所述第一衍射峰的半峰宽之和为a，N个所述第二衍射峰的半峰宽之和为b，其中，1.2≤b/a≤3.0。The sum of the half-peak widths of the M first diffraction peaks is a, and the sum of the half-peak widths of the N second diffraction peaks is b, wherein 1.2≤b/a≤3.0.
如上所述的电池，1.7≤b/a≤2.2；For a battery as described above, 1.7≤b/a≤2.2;
或，2.7≤b/a≤2.95。Or, 2.7≤b/a≤2.95.
如上所述的电池，0.8≤a≤1.4，1.2≤b≤3.5。For the battery as described above, 0.8≤a≤1.4, 1.2≤b≤3.5.
如上所述的电池，所述电池为固态电池或半固态电池。The battery as described above is a solid-state battery or a semi-solid-state battery.
如上所述的电池，所述电解质为固态电解质或半固态电解质。In the battery as described above, the electrolyte is a solid electrolyte or a semi-solid electrolyte.
如上所述的电池，所述电解质包括经聚合单体聚合得到的聚合物，所述聚合单体包括官能团，所述官能团至少包括两个丙烯酸酯基团。In the battery as described above, the electrolyte comprises a polymer obtained by polymerizing a polymerized monomer, the polymerized monomer comprises a functional group, and the functional group comprises at least two acrylate groups.
如上所述的电池，所述聚合单体包括双官能团单体、三官能团单体、四官能团单体、六官能团单体中的一种或多种。In the battery as described above, the polymerized monomer includes one or more of a bifunctional monomer, a trifunctional monomer, a tetrafunctional monomer, and a hexafunctional monomer.
如上所述的电池，所述双官能团单体包括二丙二醇二丙烯酸酯及其衍生物、聚乙二醇二丙烯酸酯及其衍生物、三丙二醇二丙烯酸酯及其衍生物、1,6-己二醇二丙烯酸酯及其衍生物、乙二醇二甲基丙烯酸酯及其衍生物、二乙二醇二甲基丙烯酸酯及其衍生物、三乙二醇二甲基丙烯酸酯及其衍生物、乙氧化双酚A二丙烯酸酯及其衍生物中的一种或多种；In the battery as described above, the bifunctional monomer includes one or more of dipropylene glycol diacrylate and its derivatives, polyethylene glycol diacrylate and its derivatives, tripropylene glycol diacrylate and its derivatives, 1,6-hexanediol diacrylate and its derivatives, ethylene glycol dimethacrylate and its derivatives, diethylene glycol dimethacrylate and its derivatives, triethylene glycol dimethacrylate and its derivatives, and ethoxylated bisphenol A diacrylate and its derivatives;
和/或，所述三官能团单体包括乙氧化三羟甲基丙烷三丙烯酸酯及其衍生物、季戊四醇三丙烯酸酯及其衍生物、三羟甲基丙烷三丙烯酸酯及其衍生物、三羟甲基丙烷三甲基丙烯酸酯及其衍生物中的一种或多种；And/or, the trifunctional monomer includes one or more of ethoxylated trimethylolpropane triacrylate and its derivatives, pentaerythritol triacrylate and its derivatives, trimethylolpropane triacrylate and its derivatives, trimethylolpropane trimethacrylate and its derivatives;
和/或，所述四官能团单体包括乙氧化(5)季戊四醇四丙烯酸酯及其衍生物；and/or, the tetrafunctional monomer comprises ethoxylated (5) pentaerythritol tetraacrylate and its derivatives;
和/或，所述六官能团单体包括二季戊四醇六丙烯酸酯及其衍生物。And/or, the hexafunctional monomer includes dipentaerythritol hexaacrylate and its derivatives.
如上所述的电池，所述电池通过包括以下过程的方法制备得到：The battery as described above is prepared by a method comprising the following steps:
将包括电解质前驱液的电池依次进行预处理、固化化成处理和化成处理，得到所述电池，所述电解质前驱液包括聚合单体；The battery is obtained by sequentially subjecting a battery including an electrolyte precursor solution to pretreatment, curing and formation treatment, and formation treatment, wherein the electrolyte precursor solution includes a polymerizable monomer;
其中，所述预处理包括：在40℃～60℃下使包括所述聚合单体的电解质前驱液进行预聚反应0.5h～2h；Wherein, the pretreatment comprises: subjecting the electrolyte precursor solution including the polymerizable monomer to a prepolymerization reaction at 40° C. to 60° C. for 0.5 h to 2 h;
所述固化化成处理包括：在60℃～80℃的温度、≤3MPa的压力、≤0.3C的倍率下，对预处理后的电池充电至3.7V；The curing treatment comprises: charging the pretreated battery to 3.7V at a temperature of 60°C to 80°C, a pressure of ≤3MPa, and a rate of ≤0.3C;
所述化成处理包括：在60℃～90℃的温度，≤3MPa的压力，≤1C的倍率下将固化化成处理后的电池充电至截止电压，截止电压≥4.0V，得到所述电池。The chemical formation treatment comprises: charging the battery after the curing chemical formation treatment to a cut-off voltage of ≥4.0V at a temperature of 60°C to 90°C, a pressure of ≤3MPa, and a rate of ≤1C to obtain the battery.
如上所述的电池，所述电解质包括0.05wt％～9wt％的聚合物和91wt％～99.5wt％的电解液。In the battery as described above, the electrolyte comprises 0.05 wt % to 9 wt % of the polymer and 91 wt % to 99.5 wt % of the electrolyte.
如上所述的电池，所述电解液包括锂盐和非水有机溶剂。In the battery as described above, the electrolyte includes a lithium salt and a non-aqueous organic solvent.
如上所述的电池，所述锂盐选自六氟磷酸锂、四氟硼酸锂、双草酸硼酸锂、双氟草酸硼酸锂、双氟双草酸磷酸锂、四氟草酸磷酸锂、二氟磷酸锂、高氯酸锂、双氟磺酰胺锂和双三氟甲基磺酰亚胺锂中的一种或多种。In the battery as described above, the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisoxalatoborate, lithium bisfluorooxalatoborate, lithium bisfluorobisoxalatophosphate, lithium tetrafluorooxalatophosphate, lithium difluorophosphate, lithium perchlorate, lithium bisfluorosulfonamide and lithium bistrifluoromethylsulfonyl imide.
如上所述的电池，所述非水有机溶剂选自环状碳酸酯、线性碳酸酯、线性羧酸酯中的一种或多种。In the battery as described above, the non-aqueous organic solvent is selected from one or more of cyclic carbonates, linear carbonates, and linear carboxylates.
如上所述的电池，还包括正极片；所述正极片包括正极活性物质，所述正极活性物质包括磷酸铁锂、钴酸锂、镍钴锰酸锂、锰酸锂、镍钴铝酸锂、镍钴锰铝酸锂、镍钴铝钨材料、富锂锰基固溶体正极材料、镍钴酸锂、镍钛镁酸锂、镍酸锂、尖晶石锰酸锂、镍钴钨、镍锰酸锂、含钠钴酸锂中的一种或多种。The battery as described above also includes a positive electrode sheet; the positive electrode sheet includes a positive electrode active material, and the positive electrode active material includes one or more of lithium iron phosphate, lithium cobalt oxide, lithium nickel cobalt manganese oxide, lithium manganese oxide, lithium nickel cobalt aluminum oxide, lithium nickel cobalt manganese aluminum oxide, nickel cobalt aluminum tungsten material, lithium-rich manganese-based solid solution positive electrode material, lithium nickel cobalt oxide, lithium nickel titanium magnesium oxide, lithium nickel oxide, spinel lithium manganese oxide, nickel cobalt tungsten, lithium nickel manganese oxide, and sodium-containing lithium cobalt oxide.
如上所述的电池，还包括负极片；所述负极片包括负极活性物质，所述负极活性物质包括硅、硅碳、SiOx、锂硅合金、硅合金、人造石墨、天然石墨、硬碳、软碳、中间相炭微球、富勒烯、石墨烯、焦炭、碳纤维、硼及其衍生物、铝及其衍生物、镁及其衍生物、铋及其衍生物、镍及其衍生物、银及其衍生物、锌及其衍生物、钛及其衍生物、镓及其衍生物、铟及其衍生物、锡及其衍生物、氮化锂、氮化铜中的一种或多种。The battery as described above also includes a negative electrode sheet; the negative electrode sheet includes a negative electrode active material, and the negative electrode active material includes one or more of silicon, silicon carbon, SiOx, lithium silicon alloy, silicon alloy, artificial graphite, natural graphite, hard carbon, soft carbon, mesophase carbon microspheres, fullerenes, graphene, coke, carbon fiber, boron and its derivatives, aluminum and its derivatives, magnesium and its derivatives, bismuth and its derivatives, nickel and its derivatives, silver and its derivatives, zinc and its derivatives, titanium and its derivatives, gallium and its derivatives, indium and its derivatives, tin and its derivatives, lithium nitride, and copper nitride.
本申请第二方面提供一种电子设备，包括上述任一所述的电池。A second aspect of the present application provides an electronic device, comprising any of the above-mentioned batteries.
本申请提供的电池，包括电解质，其随着温度的提高具有较低的失重率，表明电解质具有较好的热稳定性，能够有效延长电池的ARC热失控时间，提高电池的安全性和循环性能。The battery provided in the present application includes an electrolyte, which has a lower weight loss rate as the temperature increases, indicating that the electrolyte has good thermal stability, can effectively prolong the ARC thermal runaway time of the battery, and improve the safety and cycle performance of the battery.
图1为本申请实施例1提供的电解质的热重分析结果；FIG1 is a thermogravimetric analysis result of the electrolyte provided in Example 1 of the present application;
图2为本申请实施例4提供的电解质的热重分析结果；FIG2 is a thermogravimetric analysis result of the electrolyte provided in Example 4 of the present application;
图3为本申请实施例5提供的电解质的热重分析结果；FIG3 is a thermogravimetric analysis result of the electrolyte provided in Example 5 of the present application;
图4为本申请实施例1提供的电池的热失控分析结果；FIG4 is a thermal runaway analysis result of a battery provided in Example 1 of the present application;
图5为本申请实施例2提供的电池的热失控分析结果；FIG5 is a thermal runaway analysis result of a battery provided in Example 2 of the present application;
图6为本申请实施例3提供的电池的热失控分析结果；FIG6 is a thermal runaway analysis result of a battery provided in Example 3 of the present application;
[根据细则26改正 18.07.2023]
图7为本申请实施例4提供的电池的热失控分析结果；[Corrected 18.07.2023 in accordance with Rule 26]
FIG7 is a thermal runaway analysis result of a battery provided in Example 4 of the present application;
[根据细则26改正 18.07.2023]
图8为本申请对比例1提供的电池的热失控分析结果；[Corrected 18.07.2023 in accordance with Rule 26]
FIG8 is a thermal runaway analysis result of a battery provided in Comparative Example 1 of the present application;
[根据细则26改正 18.07.2023]
图9为本申请对比例2提供的电池的热失控分析结果。[Corrected 18.07.2023 in accordance with Rule 26]
FIG9 is a thermal runaway analysis result of the battery provided in Comparative Example 2 of the present application.
为使本申请的目的、技术方案和优点更加清楚，下面将结合本申请的实施例，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。In order to make the purpose, technical solutions and advantages of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below in combination with the embodiments of this application. Obviously, the described embodiments are part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.
本申请提供一种电池，包括电解质；The present application provides a battery, comprising an electrolyte;
在氮气气氛下，以5℃/min的升温速度对所述电解质进行热重分析，所述电解质在100℃～600℃之间至少存在一个失重峰。In a nitrogen atmosphere, a thermogravimetric analysis is performed on the electrolyte at a heating rate of 5° C./min, and the electrolyte has at least one weight loss peak between 100° C. and 600° C.
进一步地，所述电解质在100℃～600℃下的失重率为3～85％。Furthermore, the weight loss rate of the electrolyte at 100° C. to 600° C. is 3 to 85%.
进一步地，在氮气气氛下，从初始温度T0开始，以5℃/min的升温速率对所述电解质进行热重分析，初始温度T0为25℃，初始温度T0下电解质的质量为M0；Further, in a nitrogen atmosphere, starting from an initial temperature T0 , a thermogravimetric analysis of the electrolyte is performed at a heating rate of 5° C./min, the initial temperature T0 is 25° C., and the mass of the electrolyte at the initial temperature T0 is M0 ;
所述电解质满足下述至少一项：The electrolyte satisfies at least one of the following:
(1)当温度T到达100℃时，电解质的质量≥96.13％*M0；(1) When the temperature T reaches 100°C, the mass of the electrolyte is ≥96.13%*M0 ;
(2)当温度T到达200℃时，电解质的质量≥49.46％*M0；(2) When the temperature T reaches 200°C, the mass of the electrolyte is ≥49.46%*M0 ;
(3)当温度T到达300℃时，电解质的质量≥35.02％*M0；(3) When the temperature T reaches 300°C, the mass of the electrolyte is ≥35.02%*M0 ;
(4)当温度T到达400℃时，电解质的质量≥27.51％*M0；(4) When the temperature T reaches 400°C, the mass of the electrolyte is ≥ 27.51%*M0 ;
(5)当温度T到达500℃时，电解质的质量≥19.06％*M0；(5) When the temperature T reaches 500°C, the mass of the electrolyte is ≥19.06%*M0 ;
(6)当温度T到达590℃时，电解质的质量≥17.74％*M0。(6) When the temperature T reaches 590°C, the mass of the electrolyte is ≥17.74%*M0 .
本申请提供的电池包括电解质，其随着温度的提高而具有较低的失重率，表明具备较好的热稳定性。The battery provided in the present application includes an electrolyte, which has a lower weight loss rate as the temperature increases, indicating that it has good thermal stability.
需要说明的是，在对电解质进行热重分析时，需要对电解质进行预处理以除去杂质。尤其在对电池中的电解质进行分析时，需要对电池拆解，并采用去离子水对电解质进行清洗，收集固相组分，100℃烘干24小时后，对其进行热重测试。热重分析使用热重仪进行。It should be noted that when performing thermogravimetric analysis on electrolytes, the electrolytes need to be pretreated to remove impurities. In particular, when analyzing the electrolytes in batteries, the batteries need to be disassembled, the electrolytes need to be cleaned with deionized water, the solid phase components need to be collected, and after drying at 100°C for 24 hours, thermogravimetric testing is performed on them. Thermogravimetric analysis is performed using a thermogravimeter.
热重分析过程中，在初始温度T0下测试电解质的质量M0，初始温度T0为25℃，随后以5℃/min的升温速率进行升温，并在不同温度下测试电解质的质量。随着温度的不断升高，电解质的质量不断下降，但本申请提供的电解质的损失量能够保持在较小区间内，表明本申请提供的电解质具有较好的热稳定性，能够有效延长电池的ARC热失控时间，提高电池的安全性和循环性能。During the thermogravimetric analysis, the mass M0 of the electrolyte was tested at an initial temperature T0 , the initial temperature T0 was 25°C, and then the temperature was increased at a heating rate of 5°C/min, and the mass of the electrolyte was tested at different temperatures. As the temperature continued to rise, the mass of the electrolyte continued to decrease, but the loss of the electrolyte provided in the present application could be maintained within a small range, indicating that the electrolyte provided in the present application has good thermal stability, can effectively prolong the ARC thermal runaway time of the battery, and improve the safety and cycle performance of the battery.
在一种具体实施方式中，所述电解质的X射线衍射图中具有M个2θ衍射角为x的第一衍射峰和N个2θ衍射角为y的第二衍射峰，M≥1，N≥1；其中，10°≤x≤30°，30°≤y≤50°；M个所述第一衍射峰的半峰宽之和为a，N个所述第二衍射峰的半峰宽之和为b，其中，1.2≤b/a≤3.0。In a specific embodiment, the X-ray diffraction pattern of the electrolyte has M first diffraction peaks with a 2θ diffraction angle of x and N second diffraction peaks with a 2θ diffraction angle of y, M≥1, N≥1; wherein, 10°≤x≤30°, 30°≤y≤50°; the sum of the half-peak widths of the M first diffraction peaks is a, and the sum of the half-peak widths of the N second diffraction peaks is b, wherein, 1.2≤b/a≤3.0.
当电解质满足上述要求时，则表明该电解质具有特殊的结晶性能，有利于锂离子在电解质中的传导，从而使电解质具有良好的电导率，进而使包括该电解质的电池在不同倍率和不同温度下均具有良好的放电性能，表现出优异的倍率性能和温度特性，尤其是在大倍率以及低温下放电更具优势。When the electrolyte meets the above requirements, it indicates that the electrolyte has special crystallization properties, which is beneficial to the conduction of lithium ions in the electrolyte, so that the electrolyte has good electrical conductivity, and then the battery including the electrolyte has good discharge performance at different rates and temperatures, showing excellent rate performance and temperature characteristics, especially at high rates and low temperatures.
进一步地，1.7≤b/a≤2.2；或，2.7≤b/a≤2.95。Further, 1.7≤b/a≤2.2; or, 2.7≤b/a≤2.95.
进一步地，0.8≤a≤1.4，1.2≤b≤3.5。Furthermore, 0.8≤a≤1.4, 1.2≤b≤3.5.
需要说明的是，在对电解质进行X射线衍射分析时，尤其是对电池中的电解质进行分析时，在对电池拆解后，需要先对电解质进行预处理以分离除去电解质中的其他成分。预处理包括：采用去离子水对电解质进行水洗处理，水洗完成后抽真空在80℃下处理48h后，检测到水分含量＜1000ppm时，即可进行X射线衍射分析。It should be noted that when performing X-ray diffraction analysis on electrolytes, especially when analyzing electrolytes in batteries, after disassembling the battery, the electrolytes need to be pretreated to separate and remove other components in the electrolyte. The pretreatment includes: washing the electrolyte with deionized water, vacuuming and treating at 80°C for 48 hours, and when the moisture content is less than 1000ppm, X-ray diffraction analysis can be performed.
在一种具体实施方式中，电解质包括经聚合单体聚合得到的聚合物，所述聚合单体包括官能团，所述官能团至少包括两个丙烯酸酯基团。In a specific embodiment, the electrolyte includes a polymer obtained by polymerizing a polymerized monomer, wherein the polymerized monomer includes a functional group, and the functional group includes at least two acrylate groups.
进一步地，所述聚合单体选自双官能团单体、三官能团单体、四官能团单体、六官能团单体中的一种或多种。Furthermore, the polymerizable monomer is selected from one or more of a difunctional monomer, a trifunctional monomer, a tetrafunctional monomer, and a hexafunctional monomer.
具体地，双官能团单体指的是含有两个碳碳双键的聚合物单体，包括但不局限于二丙二醇二丙烯酸酯及其衍生物、聚乙二醇二丙烯酸酯及其衍生物、三丙二醇二丙烯酸酯及其衍生物、1,6-己二醇二丙烯酸酯及其衍生物、乙二醇二甲基丙烯酸酯及其衍生物、乙氧化双酚A二丙烯酸酯及其衍生物中的一种或多种。Specifically, the difunctional monomer refers to a polymer monomer containing two carbon-carbon double bonds, including but not limited to one or more of dipropylene glycol diacrylate and its derivatives, polyethylene glycol diacrylate and its derivatives, tripropylene glycol diacrylate and its derivatives, 1,6-hexanediol diacrylate and its derivatives, ethylene glycol dimethacrylate and its derivatives, and ethoxylated bisphenol A diacrylate and its derivatives.
三官能团单体指的是含有三个碳碳双键的聚合物单体，包括但不局限于乙氧化三羟甲基丙烷三丙烯酸酯及其衍生物、季戊四醇三丙烯酸酯及其衍生物、三羟甲基丙烷三丙烯酸酯及其衍生物、三羟甲基丙烷三甲基丙烯酸酯及其衍生物中的一种或多种。The trifunctional monomer refers to a polymer monomer containing three carbon-carbon double bonds, including but not limited to one or more of ethoxylated trimethylolpropane triacrylate and its derivatives, pentaerythritol triacrylate and its derivatives, trimethylolpropane triacrylate and its derivatives, and trimethylolpropane trimethacrylate and its derivatives.
四官能团单体为乙氧化(5)季戊四醇四丙烯酸酯及其衍生物；The tetrafunctional monomer is ethoxylated (5) pentaerythritol tetraacrylate and its derivatives;
六官能团单体为二季戊四醇六丙烯酸酯及其衍生物。The hexafunctional monomer is dipentaerythritol hexaacrylate and its derivatives.
需要说明的是，上述衍生物是指以新的取代基团对本体中的原基团进行取代后的产物，例如，乙氧化三羟甲基丙烷三丙烯酸酯的衍生物是指利用取代基团对乙氧化三羟甲基丙烷三丙烯酸酯中的原基团(例如氢原子)进行取代后的产物。本发明不限定取代基团的具体选择，例如可以是卤素原子、羟基、硫醇、硝基、氰基、异氰基、砜基、羟胺、羧基、羰基、芳烃、杂环芳烃、杂环烷基、氨基，烷氧基，芳环氧基，芳杂环氧基，酰胺基，烷硫基，芳环硫基，杂芳环硫基，硅基，硼基等中的至少一种。It should be noted that the above-mentioned derivatives refer to products obtained by replacing the original groups in the main body with new substituent groups. For example, the derivatives of ethoxylated trimethylolpropane triacrylate refer to products obtained by replacing the original groups (such as hydrogen atoms) in ethoxylated trimethylolpropane triacrylate with substituent groups. The present invention does not limit the specific selection of substituent groups, for example, it can be at least one of halogen atoms, hydroxyl groups, thiol groups, nitro groups, cyano groups, isocyano groups, sulfone groups, hydroxylamine groups, carboxyl groups, carbonyl groups, aromatic hydrocarbons, heteroaromatic hydrocarbons, heterocycloalkyl groups, amino groups, alkoxy groups, aromatic ring oxygen groups, aromatic heterocyclic oxygen groups, amide groups, alkylthio groups, aromatic ring sulfur groups, heteroaromatic ring sulfur groups, silicon groups, boron groups, etc.
进一步地，所述电池通过包括以下过程的方法制备得到：Furthermore, the battery is prepared by a method comprising the following processes:
将包括电解质前驱液的电池依次进行预处理、固化化成处理和化成处理，得到所述电池，所述电解质前驱液包括所述聚合单体；sequentially subjecting a battery including an electrolyte precursor solution to pretreatment, curing and formation treatment, and formation treatment to obtain the battery, wherein the electrolyte precursor solution includes the polymerized monomer;
其中，所述预处理包括：在40℃～60℃下使包括所述聚合单体的电解质前驱液进行预聚反应0.5h～2h；Wherein, the pretreatment comprises: subjecting the electrolyte precursor solution including the polymerizable monomer to a prepolymerization reaction at 40° C. to 60° C. for 0.5 h to 2 h;
所述固化化成处理包括：在60℃～80℃的温度、≤3MPa的压力、≤0.3C的倍率下，对预处理后的电池充电至3.7V；The curing treatment comprises: charging the pretreated battery to 3.7V at a temperature of 60°C to 80°C, a pressure of ≤3MPa, and a rate of ≤0.3C;
所述化成处理包括：在60℃～90℃的温度，≤3MPa的压力，≤1C的倍率下将固化化成处理后的电池充电至截止电压，截止电压≥4.0V，得到所述电池。The chemical formation treatment comprises: charging the battery after the curing chemical formation treatment to a cut-off voltage of ≥4.0V at a temperature of 60°C to 90°C, a pressure of ≤3MPa, and a rate of ≤1C to obtain the battery.
本申请通过预处理-固化化成处理-化成处理，有助于得到具有较好热稳定性的电解质，聚合单体具有可反应基团，在预处理过程中，可进行聚合固化反应，形成初步电解质骨架结构；随后在固化化成处理过程中，聚合单体进行进一步固化，形成电解质并去除未反应的聚合单体，并同时进行化成处理，有助于在电池内部形成热稳定好的的电解质，随后再进行化成处理，得到电解质，本发明提供的方法有助于提高电解质的热稳定性，延长电池的ARC热失控时间，使电池具有更高的安全性能。The present application helps to obtain an electrolyte with good thermal stability through pretreatment-curing chemical formation treatment-chemical formation treatment. The polymerized monomer has a reactive group. During the pretreatment process, a polymerization curing reaction can be carried out to form a preliminary electrolyte skeleton structure; then during the curing chemical formation treatment, the polymerized monomer is further cured to form an electrolyte and remove the unreacted polymerized monomer, and a chemical formation treatment is carried out at the same time, which helps to form a thermally stable electrolyte inside the battery, and then a chemical formation treatment is carried out to obtain an electrolyte. The method provided by the present invention helps to improve the thermal stability of the electrolyte, prolong the ARC thermal runaway time of the battery, and make the battery have higher safety performance.
可以理解，电解质前驱液中还包括引发聚合单体聚合的引发剂，具体地，引发剂包括但不局限于过氧化苯甲酰、过氧化苯甲酰叔丁酯、过氧化月桂酰、过氧化苯甲酰叔丁酯、偶氮二异丁腈、过氧化叔戊酸叔丁基酯、过氧化苯甲酸叔丁酯中的一种或多种。It can be understood that the electrolyte precursor solution also includes an initiator for initiating the polymerization of the polymerization monomer. Specifically, the initiator includes but is not limited to one or more of benzoyl peroxide, tert-butyl benzoyl peroxide, lauroyl peroxide, tert-butyl benzoyl peroxide, azobisisobutyronitrile, tert-butyl peroxyvalerate, and tert-butyl perbenzoate.
在一种具体的实施方式中，所述电池为半固态电池，电解质包括0.05wt％～9wt％的聚合物和91wt％～99.5wt％的电解液。In a specific embodiment, the battery is a semi-solid battery, and the electrolyte comprises 0.05 wt % to 9 wt % of a polymer and 91 wt % to 99.5 wt % of an electrolyte.
可以理解，当电池为半固态电池时，电解质前驱液中还包括电解液所需的组分，具体地，电解液包括锂盐和非水有机溶剂。It can be understood that when the battery is a semi-solid battery, the electrolyte precursor solution also includes components required for the electrolyte. Specifically, the electrolyte includes a lithium salt and a non-aqueous organic solvent.
锂盐可选自本领域常规使用的电解液锂盐，包括但不局限于六氟磷酸锂、四氟硼酸锂、双草酸硼酸锂、双氟草酸硼酸锂、双氟双草酸磷酸锂、四氟草酸磷酸锂、二氟磷酸锂、高氯酸锂、双氟磺酰胺锂和双三氟甲基磺酰亚胺锂中的一种或多种。The lithium salt can be selected from the electrolyte lithium salts commonly used in the art, including but not limited to one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bisoxalatoborate, lithium bisfluorooxalatoborate, lithium bisoxalatophosphate, lithium tetrafluorooxalatophosphate, lithium difluorophosphate, lithium perchlorate, lithium bisfluorosulfonamide and lithium bistrifluoromethylsulfonyl imide.
在一种具体的实施方式中，所述非水有机溶剂选自环状碳酸酯、线性碳酸酯、线性羧酸酯中的一种或多种。In a specific embodiment, the non-aqueous organic solvent is selected from one or more of cyclic carbonates, linear carbonates, and linear carboxylates.
其中，环状碳酸酯选自碳酸乙烯酯和碳酸丙烯酯中的一种或多种，线性碳酸酯选自碳酸二甲酯、碳酸二乙酯和碳酸甲乙酯中的一种或多种，线性羧酸酯选自丙酸乙酯、丙酸丙酯和乙酸丙酯中的一种或多种。Among them, the cyclic carbonate is selected from one or more of ethylene carbonate and propylene carbonate, the linear carbonate is selected from one or more of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, and the linear carboxylic acid ester is selected from one or more of ethyl propionate, propyl propionate and propyl acetate.
在一种具体的实施方式中，非水有机溶剂中的环状碳酸酯中的质量含量为20～60wt％，线性碳酸酯和/或线性羧酸酯的质量含量为40～80wt％。In a specific embodiment, the mass content of the cyclic carbonate in the non-aqueous organic solvent is 20-60 wt %, and the mass content of the linear carbonate and/or linear carboxylic acid ester is 40-80 wt %.
此外，锂盐电解液中还包括添加剂，添加剂可根据本领域常规技术手段进行添加，以改善电池的综合性能，例如，添加剂选自碳酸亚乙烯酯、氟代碳酸乙烯酯、双氟代碳酸乙烯酯、硫酸乙烯酯、1,3-丙烯磺酸内酯、二氟磷酸锂、双草酸硼酸锂、有机磷化物、有机氟化物、氟代烷基磷酸酯中的一种或多种。In addition, the lithium salt electrolyte also includes additives, which can be added according to conventional technical means in the art to improve the comprehensive performance of the battery. For example, the additives are selected from one or more of vinylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate, vinyl sulfate, 1,3-propylene sultone, lithium difluorophosphate, lithium bis(oxalatoborate), organic phosphides, organic fluorides, and fluoroalkyl phosphates.
此外，本申请的电池中，除电解质外，还包括正极极片、负极极片和隔膜。In addition, the battery of the present application, in addition to the electrolyte, also includes a positive electrode sheet, a negative electrode sheet and a separator.
具体地，正极极片包括正极集流体和设置在正极集流体表面的正极活性物质层，正极极片的材料可以为本领域常规材料，例如，正极集流体可以为铝箔等常规金属箔材；正极活性物质层包括正极活性物质、导电剂、粘结剂和添加剂。Specifically, the positive electrode plate includes a positive electrode current collector and a positive electrode active material layer arranged on the surface of the positive electrode current collector. The material of the positive electrode plate can be a conventional material in the art. For example, the positive electrode current collector can be a conventional metal foil such as aluminum foil; the positive electrode active material layer includes a positive electrode active material, a conductive agent, a binder and additives.
其中，正极活性物质可选自磷酸铁锂(LiFePO4)、钴酸锂(LiCoO2)、镍钴锰酸锂(LizNixCoyMn1-x-yO2，其中0.95≤z≤1.05，x>0，y>0，0<x+y<1)、锰酸锂(LiMnO2)、镍钴铝酸锂(LizNixCoyAl1-x-yO2，其中0.95≤z≤1.05，x>0，y>0，0.8≤x+y<1)、镍钴锰铝酸锂(LizNixCoyMnwAl1-x-y-wO2，其中0.95≤z≤1.05，x>0，y>0，w>0，0.8≤x+y+w<1)、镍钴铝钨材料、富锂锰基固溶体正极材料(xLi2MnO3·(1-x)LiMO2，其中M＝Ni/Co/Mn)、镍钴酸锂(LiNixCoyO2，其中x>0，y>0，x+y＝1)、镍钛镁酸锂(LiNixTiyMgzO2，其中，x>0，y>0，z>0，x+y+z＝1)、镍酸锂(Li2NiO2)、尖晶石锰酸锂(LiMn2O4)、镍钴钨、镍锰酸锂、含钠钴酸锂(Lin1-y1Nay1Co1-a1-b1M1b1M2a1O2或者Lin2-y2-b2Nay2Co1-a2M1b2M2a2O2，0.6≤n1≤0.8，0＜y1≤0.05，0≤a1≤0.1，0＜b1≤0.1，0<b1/1-a1-b1<0.1；0.6≤n2≤0.8，0＜y2≤0.05，0≤a2≤0.1，0＜b2≤0.02；M1选自Te、W、Al、B、P以及K中的至少一种；M2为Mg、Zr、Y、La、Ni等不同于M1的掺杂元素)中的一种或多种。The positive electrode active material may be selected from lithium iron phosphate (LiFePO4 ), lithium cobalt oxide (LiCoO2 ), lithium nickel cobalt manganese oxide (Liz Nix Coy Mn1-xy O2 , wherein 0.95≤z≤1.05, x>0, y>0, 0<x+y<1), lithium manganese oxide (LiMnO2 ), lithium nickel cobalt aluminum oxide (Liz Nix Coy Al1-xy O2 , wherein 0.95≤z≤1.05, x>0, y>0, 0.8≤x+y<1), lithium nickel cobalt manganese aluminum oxide (Liz Nix Coy Mnw Al1-xyw O2 , wherein 0.95≤z≤1.05, x>0, y>0, w>0, 0.8≤x+y+w<1), nickel cobalt aluminum tungsten material, lithium-rich manganese-based solid solution positive electrode material (xLi2 MnO3 (1-x)LiMO2 , wherein M=Ni/Co/Mn), lithium nickel cobalt oxide (LiNix Coy O2 , wherein x>0, y>0, x+y=1), lithium nickel titanium magnesium oxide (LiNix Tiy Mgz O2 , wherein x>0, y>0, z>0, x+y+z=1), lithium nickel oxide (Li2 NiO2 ), spinel lithium manganese oxide (LiMn2 O4 ), nickel cobalt tungsten, lithium nickel manganese oxide, sodium-containing lithium cobalt oxide (Lin1-y1 Nay1 Co1-a1-b1 M1b1 M2a1 O2 or Lin2-y2-b2 Nay2 Co1-a2 M1b2 M2a 2O2 , 0.6≤n1≤0.8, 0＜y1≤0.05, 0≤a1≤0.1, 0＜b1≤0.1, 0<b1/1-a1-b1<0.1; 0.6≤n2≤0.8, 0＜y2≤0.05, 0≤a2≤0.1, 0＜b2≤0.02; M1 is selected from at least one of Te, W, Al, B, P and K; M2 is one or more of Mg, Zr, Y, La, Ni and other doping elements different from M1).
负极极片包括负极集流体和设置在负极集流体表面的负极活性物质层，负极集流体可选自本领域中常规使用的负极集流体，如铜箔等。负极活性物质层中包括负极活性物质、导电剂、粘结剂和添加剂。The negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer disposed on the surface of the negative electrode current collector. The negative electrode current collector can be selected from the negative electrode current collectors commonly used in the art, such as copper foil, etc. The negative electrode active material layer includes negative electrode active materials, conductive agents, binders and additives.
其中，负极活性物质可选自硅、硅碳、SiOx(0＜X＜2)、锂硅合金、硅合金、人造石墨、天然石墨、硬碳、软碳、中间相炭微球、富勒烯、石墨烯、焦炭、碳纤维、硼及其衍生物(如硼粉、氧化硼)、铝及其衍生物(如铝粉、锂铝合金)、镁及其衍生物(如镁、镁铝合金)、铋及其衍生物(如铋、锂铋合金)、镍及其衍生物(如镍、锂镍合金、氮镍化锂)、银及其衍生物(如银粉、锂银合金)、锌及其衍生物(如锌粉、锌锂合金、氮化锌)、钛及其衍生物(如钛粉、钛酸锂、二氧化钛、锂钛合金等)、镓及其衍生物(如镓、锂镓合金)、铟及其衍生物(如铟粉、锂铟合金)、锡及其衍生物(如锡粉、氧化亚锡、氧化锡、硫酸锡)、氮化锂、氮化铜中的至少一种。Among them, the negative electrode active material can be selected from at least one of silicon, silicon carbon, SiOx (0＜X＜2), lithium silicon alloy, silicon alloy, artificial graphite, natural graphite, hard carbon, soft carbon, mesophase carbon microspheres, fullerene, graphene, coke, carbon fiber, boron and its derivatives (such as boron powder, boron oxide), aluminum and its derivatives (such as aluminum powder, lithium aluminum alloy), magnesium and its derivatives (such as magnesium, magnesium aluminum alloy), bismuth and its derivatives (such as bismuth, lithium bismuth alloy), nickel and its derivatives (such as nickel, lithium nickel alloy, lithium nickel nitride), silver and its derivatives (such as silver powder, lithium silver alloy), zinc and its derivatives (such as zinc powder, zinc lithium alloy, zinc nitride), titanium and its derivatives (such as titanium powder, lithium titanate, titanium dioxide, lithium titanium alloy, etc.), gallium and its derivatives (such as gallium, lithium gallium alloy), indium and its derivatives (such as indium powder, lithium indium alloy), tin and its derivatives (such as tin powder, stannous oxide, tin oxide, tin sulfate), lithium nitride, and copper nitride.
本申请提供的电池的制备方法可以按照本领域常规方法进行制备。The preparation method of the battery provided in this application can be prepared according to conventional methods in the art.
在一种具体的实施方式中，首先，制备得到正极极片和负极极片，其中，正极极片的制备方法包括：将正极活性材料、粘结剂、导电剂和添加剂混合后，加入溶剂(例如N-甲基吡咯烷酮)，在真空搅拌机作用下进行搅拌，直至混合得到具有均一流动性的正极浆料，再将正极浆料涂覆在正极集流体的单侧或者双侧，在室温晾干后转移至烘箱中烘干，然后经过冷压、分切得到正极极片。负极片的制备方法包括：将负极活性材料、粘结剂、导电剂和添加剂混合后，加入溶剂(例如去离子水)，在真空搅拌机作用下获得负极浆料，再将负极浆料均匀涂覆在负极集流体的单侧或者双侧，在室温晾干后转移至烘箱中烘干，然后经过冷压、分切得到负极极片。In a specific embodiment, first, a positive electrode sheet and a negative electrode sheet are prepared, wherein the preparation method of the positive electrode sheet comprises: after mixing the positive electrode active material, the binder, the conductive agent and the additive, adding a solvent (such as N-methylpyrrolidone), stirring under the action of a vacuum mixer until the mixture is mixed to obtain a positive electrode slurry with uniform fluidity, then coating the positive electrode slurry on one side or both sides of the positive electrode collector, transferring it to an oven for drying after drying at room temperature, and then cold pressing and cutting to obtain a positive electrode sheet. The preparation method of the negative electrode sheet comprises: after mixing the negative electrode active material, the binder, the conductive agent and the additive, adding a solvent (such as deionized water), obtaining a negative electrode slurry under the action of a vacuum mixer, then uniformly coating the negative electrode slurry on one side or both sides of the negative electrode collector, transferring it to an oven for drying after drying at room temperature, and then cold pressing and cutting to obtain a negative electrode sheet.
将正极极片、隔膜和负极极片依次层叠并组装得到电芯，将电芯至于外包装中，加入电解质前驱液，经封装、预处理、固化、化成等工序后制备得到电池。The positive electrode sheet, the separator and the negative electrode sheet are stacked and assembled in sequence to obtain a battery cell, the battery cell is placed in an outer package, an electrolyte precursor solution is added, and a battery is prepared after packaging, pretreatment, curing, formation and other processes.
以下将结合具体的实施例对本申请提供的电池进行详细地阐述。The battery provided in this application will be described in detail below in conjunction with specific embodiments.
实施例1Example 1
本实施例提供的电池的制备方法如下：The preparation method of the battery provided in this embodiment is as follows:
1)正极片的制备1) Preparation of positive electrode
将正极活性材料镍钴锰酸锂(镍钴锰8:1:1)、粘结剂聚偏氟乙烯、导电剂碳纳米管和导电剂SP，按照重量比为96.5：2：0.5：1进行混合，加入N-甲基吡咯烷酮，在真空搅拌机下进行搅拌，得到固含量为65％的正极浆料；将正极浆料涂覆于铝箔的两侧，在室温下晾干后转移至80℃烘箱干燥10h，然后经过冷压、分切得到正极片。The positive electrode active material lithium nickel cobalt manganese oxide (nickel cobalt manganese 8:1:1), the binder polyvinylidene fluoride, the conductive agent carbon nanotubes and the conductive agent SP are mixed in a weight ratio of 96.5:2:0.5:1, N-methylpyrrolidone is added, and the mixture is stirred under a vacuum mixer to obtain a positive electrode slurry with a solid content of 65%; the positive electrode slurry is coated on both sides of an aluminum foil, dried at room temperature, and then transferred to an oven at 80°C for drying for 10 hours, and then cold pressed and cut to obtain a positive electrode sheet.
2)负极片的制备2) Preparation of negative electrode
将负极活性材料石墨、负极活性物质硅碳、粘结剂PAA、粘结剂SBR、导电剂CNT和导电剂SP，按照重量比为45:45:3:3:2:2进行混合，加入去离子水，在真空搅拌机下进行搅拌，得到固含量为35％的负极浆料；将负极浆料涂覆于铜箔的两侧，在室温下晾干后转移至80℃烘箱干燥10h，然后经过冷压、分切后得到负极片。The negative electrode active material graphite, the negative electrode active material silicon carbon, the binder PAA, the binder SBR, the conductive agent CNT and the conductive agent SP are mixed in a weight ratio of 45:45:3:3:2:2, deionized water is added, and the mixture is stirred under a vacuum mixer to obtain a negative electrode slurry with a solid content of 35%; the negative electrode slurry is coated on both sides of the copper foil, dried at room temperature, and then transferred to an oven at 80°C for drying for 10 hours, and then cold pressed and cut to obtain a negative electrode sheet.
3)电解质前驱液的制备3) Preparation of electrolyte precursor solution
将3％乙二醇二甲基丙烯酸酯、2％三乙二醇二甲基丙烯酸酯、0.05％过氧化苯甲酰、25％碳酸丙烯酯(PC)、15％碳酸乙烯酯(EC)、15％碳酸二乙酯(DEC)、25％碳酸甲基乙基酯(EMC)、12.05％氟代碳酸乙烯酯(FEC)、2.9％碳酸亚乙烯酯(VC)，按照质量比均匀混合得到透明液体，往透明液体里面添加六氟磷酸锂和双三氟甲基磺酰亚胺锂(7:1)，进行溶解，最后达到锂盐浓度为1.45mol/L的半电解质前驱液。3% ethylene glycol dimethacrylate, 2% triethylene glycol dimethacrylate, 0.05% benzoyl peroxide, 25% propylene carbonate (PC), 15% ethylene carbonate (EC), 15% diethyl carbonate (DEC), 25% ethyl methyl carbonate (EMC), 12.05% fluoroethylene carbonate (FEC), and 2.9% vinylene carbonate (VC) are uniformly mixed in a mass ratio to obtain a transparent liquid, and lithium hexafluorophosphate and lithium bistrifluoromethylsulfonyl imide (7:1) are added to the transparent liquid for dissolution to finally obtain a semi-electrolyte precursor solution with a lithium salt concentration of 1.45 mol/L.
4)电池的组装4) Battery assembly
将正极极片、隔膜和负极极片依次层叠并组装得到电芯，将电芯至于外包装中，加入电解质前驱液，经封装、预处理、固化化成、化成等工序后制备得到电池；The positive electrode sheet, the separator and the negative electrode sheet are sequentially stacked and assembled to obtain a battery cell, the battery cell is placed in an outer package, an electrolyte precursor solution is added, and a battery is prepared after packaging, pretreatment, curing, formation and other processes;
其中，所述预处理包括：在60℃的温度下进行预聚反应0.5h；随后，在80℃的温度、3MPa的压力下，0.3C对预处理后的电池充电至3.7V；在80℃的温度，3MPa的压力，1C的倍率下将固化化成处理后的电池充电至截止电压4.25V，得到电池。The pretreatment includes: performing a prepolymerization reaction at a temperature of 60°C for 0.5h; then, charging the pretreated battery to 3.7V at 0.3C at a temperature of 80°C and a pressure of 3MPa; charging the cured battery to a cutoff voltage of 4.25V at a temperature of 80°C, a pressure of 3MPa, and a rate of 1C to obtain a battery.
实施例2Example 2
本实施例提供的电池可参考实施例1，区别在于电解质前驱液组成不同。电解质前驱液包括5.4％乙二醇二甲基丙烯酸酯、3.6％三乙二醇二甲基丙烯酸酯、0.09％过氧化苯甲酰、23.96％碳酸丙烯酯(PC)、14.38％碳酸乙烯酯(EC)、14.38％碳酸二乙酯(DEC)、23.96％碳酸甲基乙基酯(EMC)、11.55％氟代碳酸乙烯酯(FEC)、2.78％碳酸亚乙烯酯(VC)，按照质量比均匀混合得到透明液体，往透明液体里面，添加六氟磷酸锂和双三氟甲基磺酰亚胺锂(7:1)，进行溶解，最后达到锂盐浓度为1.45mol/L的电解质前驱液。The battery provided in this embodiment can refer to Example 1, except that the electrolyte precursor solution has a different composition. The electrolyte precursor solution includes 5.4% ethylene glycol dimethacrylate, 3.6% triethylene glycol dimethacrylate, 0.09% benzoyl peroxide, 23.96% propylene carbonate (PC), 14.38% ethylene carbonate (EC), 14.38% diethyl carbonate (DEC), 23.96% methyl ethyl carbonate (EMC), 11.55% fluoroethylene carbonate (FEC), and 2.78% vinylene carbonate (VC), and is uniformly mixed according to the mass ratio to obtain a transparent liquid, and lithium hexafluorophosphate and lithium bistrifluoromethylsulfonyl imide (7:1) are added to the transparent liquid to dissolve, and finally the electrolyte precursor solution with a lithium salt concentration of 1.45 mol/L is reached.
实施例3Example 3
本实施例提供的电池可参考实施例1，区别在于固化和化成阶段的差异，固化和化成阶段信息包括其中，所述预处理包括：在40℃的温度下进行预聚反应2h；随后，在80℃的温度、3MPa的压力下，0.3C对预处理后的电池充电至3.7V；在80℃的温度，0.1MPa的压力，0.5C的倍率下将固化化成处理后的电池充电至截止电压4.25V，得到电池。The battery provided in this embodiment can refer to Example 1, the difference lies in the difference in the curing and formation stages, and the curing and formation stage information includes that the pretreatment includes: carrying out a prepolymerization reaction at a temperature of 40°C for 2 hours; then, charging the pretreated battery to 3.7V at 0.3C at a temperature of 80°C and a pressure of 3MPa; charging the cured and formed battery to a cut-off voltage of 4.25V at a temperature of 80°C, a pressure of 0.1MPa, and a rate of 0.5C to obtain a battery.
实施例4Example 4
本实施例提供的电池的制备方法如下：The preparation method of the battery provided in this embodiment is as follows:
1)正极片的制备1) Preparation of positive electrode
将镍钴锰酸锂(镍钴锰9:0.5:0.5)、粘结剂聚偏氟乙烯、导电剂碳纳米管和导电剂SP，按照重量比为96.5：2：0.5：1进行混合，加入N-甲基吡咯烷酮，在真空搅拌机下进行搅拌，得到固含量为65％的正极浆料；将正极浆料涂覆于铝箔的两侧，在室温下晾干后转移至80℃烘箱干燥10h，然后经过冷压、分切得到正极片。Lithium nickel cobalt manganese oxide (nickel cobalt manganese 9:0.5:0.5), binder polyvinylidene fluoride, conductive agent carbon nanotubes and conductive agent SP are mixed in a weight ratio of 96.5:2:0.5:1, N-methylpyrrolidone is added, and the mixture is stirred under a vacuum mixer to obtain a positive electrode slurry with a solid content of 65%; the positive electrode slurry is coated on both sides of an aluminum foil, dried at room temperature, and then transferred to an oven at 80°C for drying for 10 hours, and then cold pressed and cut to obtain a positive electrode sheet.
2)负极片的制备2) Preparation of negative electrode
将负极活性材料石墨、负极活性物质硅碳、粘结剂PAA、粘结剂SBR、导电剂CNT和导电剂SP，按照重量比为80:10:3:3:2:2进行混合，加入去离子水，在真空搅拌机下进行搅拌，得到固含量为35％的负极浆料；将负极浆料涂覆于铜箔的两侧，在室温下晾干后转移至80℃烘箱干燥10h，然后经过冷压、分切后得到负极片。The negative electrode active material graphite, the negative electrode active material silicon carbon, the binder PAA, the binder SBR, the conductive agent CNT and the conductive agent SP are mixed in a weight ratio of 80:10:3:3:2:2, deionized water is added, and the mixture is stirred under a vacuum mixer to obtain a negative electrode slurry with a solid content of 35%; the negative electrode slurry is coated on both sides of the copper foil, dried at room temperature, and then transferred to an oven at 80°C for drying for 10 hours, and then cold pressed and cut to obtain a negative electrode sheet.
3)电解质前驱液的制备3) Preparation of electrolyte precursor solution
将3％乙二醇二甲基丙烯酸酯、2％三乙二醇二甲基丙烯酸酯、0.05％偶氮二异丁腈、25％碳酸丙烯酯(PC)、15％碳酸乙烯酯(EC)、15％碳酸二乙酯(DEC)、25％碳酸甲基乙基酯(EMC)、12.05％氟代碳酸乙烯酯(FEC)、2.9％碳酸亚乙烯酯(VC)，按照质量比均匀混合得到透明液体，往透明液体里面，添加六氟磷酸锂和双三氟甲基磺酰亚胺锂(7:1)，进行溶解，最后达到锂盐浓度为1.45mol/L的电解质前驱液。3% ethylene glycol dimethacrylate, 2% triethylene glycol dimethacrylate, 0.05% azobisisobutyronitrile, 25% propylene carbonate (PC), 15% ethylene carbonate (EC), 15% diethyl carbonate (DEC), 25% methyl ethyl carbonate (EMC), 12.05% fluoroethylene carbonate (FEC), and 2.9% vinylene carbonate (VC) are uniformly mixed in a mass ratio to obtain a transparent liquid. Lithium hexafluorophosphate and lithium bistrifluoromethylsulfonyl imide (7:1) are added to the transparent liquid for dissolution to finally obtain an electrolyte precursor solution with a lithium salt concentration of 1.45 mol/L.
4)电池的组装4) Battery assembly
将正极极片、隔膜和负极极片依次层叠并组装得到电芯，将电芯至于外包装中，加入电解质前驱液，经封装、预处理、固化化成、化成等工序后制备得到The positive electrode sheet, the separator and the negative electrode sheet are stacked and assembled in sequence to obtain a battery cell, the battery cell is placed in an outer package, an electrolyte precursor solution is added, and the battery cell is prepared after packaging, pretreatment, curing, and formation.
电池；Battery;
其中，所述预处理包括：在40℃的温度下进行预聚反应2h；随后，在80℃的温度、3MPa的压力下，0.3C对预处理后的电池充电至3.7V；在90℃的温度，0.1MPa的压力，0.5C的倍率下将固化化成处理后的电池充电至截止电压4.25V，得到电池。The pretreatment includes: performing a prepolymerization reaction at a temperature of 40°C for 2 hours; then, charging the pretreated battery to 3.7V at 0.3C at a temperature of 80°C and a pressure of 3MPa; charging the cured battery to a cutoff voltage of 4.25V at a temperature of 90°C, a pressure of 0.1MPa, and a rate of 0.5C to obtain a battery.
实施例5Example 5
本实施例提供的电池的制备方法如下：The preparation method of the battery provided in this embodiment is as follows:
1)正极片的制备1) Preparation of positive electrode
将钴酸锂、粘结剂聚偏氟乙烯、导电剂碳纳米管和导电剂SP，按照重量比为96.5：2：0.5：1进行混合，加入N-甲基吡咯烷酮，在真空搅拌机下进行搅拌，得到固含量为65％的正极浆料；将正极浆料涂覆于铝箔的两侧，在室温下晾干后转移至80℃烘箱干燥10h，然后经过冷压、分切得到正极片。Lithium cobalt oxide, binder polyvinylidene fluoride, conductive agent carbon nanotube and conductive agent SP are mixed in a weight ratio of 96.5:2:0.5:1, N-methylpyrrolidone is added, and the mixture is stirred under a vacuum mixer to obtain a positive electrode slurry with a solid content of 65%. The positive electrode slurry is coated on both sides of an aluminum foil, dried at room temperature, and then transferred to an oven at 80°C for drying for 10 hours, and then cold pressed and cut to obtain a positive electrode sheet.
2)负极片的制备2) Preparation of negative electrode
将负极活性材料石墨、负极活性物质硅碳、粘结剂PAA、粘结剂SBR、导电剂CNT和导电剂SP，按照重量比为95:5:3:3:2:2进行混合，加入去离子水，在真空搅拌机下进行搅拌，得到固含量为35％的负极浆料；将负极浆料涂覆于铜箔的两侧，在室温下晾干后转移至80℃烘箱干燥10h，然后经过冷压、分切后得到负极片。The negative electrode active material graphite, the negative electrode active material silicon carbon, the binder PAA, the binder SBR, the conductive agent CNT and the conductive agent SP are mixed in a weight ratio of 95:5:3:3:2:2, deionized water is added, and the mixture is stirred under a vacuum mixer to obtain a negative electrode slurry with a solid content of 35%; the negative electrode slurry is coated on both sides of the copper foil, dried at room temperature, and then transferred to an oven at 80°C for drying for 10 hours, and then cold pressed and cut to obtain a negative electrode sheet.
3)电解质前驱液的制备3) Preparation of electrolyte precursor solution
将2％三丙二醇二丙烯酸酯、2％三羟甲基丙烷三丙烯酸酯、0.04％过氧化叔戊酸叔丁基酯、25％碳酸丙烯酯(PC)、15％碳酸乙烯酯(EC)、15％碳酸二乙酯(DEC)、25％碳酸甲基乙基酯(EMC)、13.06％氟代碳酸乙烯酯(FEC)、2.9％碳酸亚乙烯酯(VC)，按照质量比均匀混合得到透明液体，往透明液体里面，添加六氟磷酸锂和双三氟甲基磺酰亚胺锂(10:1)，进行溶解，最后达到锂盐浓度为1.45mol/L的电解质前驱液。2% tripropylene glycol diacrylate, 2% trimethylolpropane triacrylate, 0.04% tert-butyl peroxypentylate, 25% propylene carbonate (PC), 15% ethylene carbonate (EC), 15% diethyl carbonate (DEC), 25% ethyl methyl carbonate (EMC), 13.06% fluoroethylene carbonate (FEC), and 2.9% vinylene carbonate (VC) are uniformly mixed in a mass ratio to obtain a transparent liquid. Lithium hexafluorophosphate and lithium bistrifluoromethylsulfonyl imide (10:1) are added to the transparent liquid for dissolution to finally obtain an electrolyte precursor solution with a lithium salt concentration of 1.45 mol/L.
4)电池的组装4) Battery assembly
将正极极片、隔膜和负极极片依次层叠并组装得到电芯，将电芯至于外包装中，加入电解质前驱液，经封装、预处理、固化化成、化成等工序后制备得到电池；The positive electrode sheet, the separator and the negative electrode sheet are sequentially stacked and assembled to obtain a battery cell, the battery cell is placed in an outer package, an electrolyte precursor solution is added, and a battery is prepared after packaging, pretreatment, curing, formation and other processes;
其中，所述预处理包括：在50℃的温度下进行预聚反应1h；随后，在70℃的温度、1MPa的压力下，0.3C对预处理后的电池充电至4.1V；在85℃的温度，0.5MPa的压力，0.5C的倍率下将固化化成处理后的电池充电至截止电压4.5V，得到电池。The pretreatment includes: performing a prepolymerization reaction at a temperature of 50°C for 1 hour; then, charging the pretreated battery to 4.1V at 0.3C at a temperature of 70°C and a pressure of 1MPa; charging the cured battery to a cutoff voltage of 4.5V at a temperature of 85°C, a pressure of 0.5MPa, and a rate of 0.5C to obtain a battery.
实施例6Example 6
本实施例提供的电池的制备方法如下：The preparation method of the battery provided in this embodiment is as follows:
1)正极片的制备1) Preparation of positive electrode
将磷酸铁锂、粘结剂聚偏氟乙烯、导电剂碳纳米管和导电剂SP，按照重量比为96.5：2：0.5：1进行混合，加入N-甲基吡咯烷酮，在真空搅拌机下进行搅拌，得到固含量为65％的正极浆料；将正极浆料涂覆于铝箔的两侧，在室温下晾干后转移至80℃烘箱干燥10h，然后经过冷压、分切得到正极片。Lithium iron phosphate, binder polyvinylidene fluoride, conductive agent carbon nanotubes and conductive agent SP are mixed in a weight ratio of 96.5:2:0.5:1, N-methylpyrrolidone is added, and the mixture is stirred under a vacuum mixer to obtain a positive electrode slurry with a solid content of 65%. The positive electrode slurry is coated on both sides of an aluminum foil, dried at room temperature, and then transferred to an oven at 80°C for drying for 10 hours, and then cold pressed and cut to obtain a positive electrode sheet.
2)负极片的制备2) Preparation of negative electrode
将负极活性材料石墨、负极活性物质硅碳、粘结剂PAA、粘结剂SBR、导电剂CNT和导电剂SP，按照重量比为80:10:3:3:2:2进行混合，加入去离子水，在真空搅拌机下进行搅拌，得到固含量为35％的负极浆料；将负极浆料涂覆于铜箔的两侧，在室温下晾干后转移至80℃烘箱干燥10h，然后经过冷压、分切后得到负极片。The negative electrode active material graphite, the negative electrode active material silicon carbon, the binder PAA, the binder SBR, the conductive agent CNT and the conductive agent SP are mixed in a weight ratio of 80:10:3:3:2:2, deionized water is added, and the mixture is stirred under a vacuum mixer to obtain a negative electrode slurry with a solid content of 35%; the negative electrode slurry is coated on both sides of the copper foil, dried at room temperature, and then transferred to an oven at 80°C for drying for 10 hours, and then cold pressed and cut to obtain a negative electrode sheet.
3)电解质前驱液的制备3) Preparation of electrolyte precursor solution
将4％三羟甲基丙烷三丙烯酸酯、1％二季戊四醇六丙烯酸酯、0.05％过氧化苯甲酰、25％碳酸丙烯酯(PC)、15％碳酸乙烯酯(EC)、15％碳酸二乙酯(DEC)、25％碳酸甲基乙基酯(EMC)、12.05％氟代碳酸乙烯酯(FEC)、2.9％碳酸亚乙烯酯(VC)，按照质量比均匀混合得到透明液体，往透明液体里面，添加六氟磷酸锂和双三氟甲基磺酰亚胺锂(8.5:1)，进行溶解，最后达到锂盐浓度为1.45mol/L的电解质前驱液。4% trimethylolpropane triacrylate, 1% dipentaerythritol hexaacrylate, 0.05% benzoyl peroxide, 25% propylene carbonate (PC), 15% ethylene carbonate (EC), 15% diethyl carbonate (DEC), 25% methyl ethyl carbonate (EMC), 12.05% fluoroethylene carbonate (FEC), and 2.9% vinylene carbonate (VC) are uniformly mixed in a mass ratio to obtain a transparent liquid. Lithium hexafluorophosphate and lithium bistrifluoromethylsulfonyl imide (8.5:1) are added into the transparent liquid to dissolve, and finally an electrolyte precursor solution with a lithium salt concentration of 1.45 mol/L is obtained.
4)电池的组装4) Battery assembly
将正极极片、隔膜和负极极片依次层叠并组装得到电芯，将电芯至于外包装中，加入电解质前驱液，经封装、预处理、固化化成、化成等工序后制备得到电池；The positive electrode sheet, the separator and the negative electrode sheet are sequentially stacked and assembled to obtain a battery cell, the battery cell is placed in an outer package, an electrolyte precursor solution is added, and a battery is prepared after packaging, pretreatment, curing, formation and other processes;
其中，所述预处理包括：在60℃的温度下进行预聚反应1.5h；随后，在80℃的温度、2MPa的压力下，0.2C对预处理后的电池充电至3.7V；在90℃的温度，0.1MPa的压力，0.5C的倍率下将固化化成处理后的电池充电至截止电压4.1V，得到电池。The pretreatment includes: performing a prepolymerization reaction at a temperature of 60°C for 1.5 hours; then, charging the pretreated battery to 3.7V at 0.2C at a temperature of 80°C and a pressure of 2MPa; charging the cured battery to a cutoff voltage of 4.1V at a temperature of 90°C, a pressure of 0.1MPa, and a rate of 0.5C to obtain a battery.
实施例7Example 7
本实施例提供的电池的制备方法如下：The preparation method of the battery provided in this embodiment is as follows:
1)正极片的制备1) Preparation of positive electrode
将磷酸锰铁锂、粘结剂聚偏氟乙烯、导电剂碳纳米管和导电剂SP，按照重量比为96.5：2：0.5：1进行混合，加入N-甲基吡咯烷酮，在真空搅拌机下进行搅拌，得到固含量为65％的正极浆料；将正极浆料涂覆于铝箔的两侧，在室温下晾干后转移至80℃烘箱干燥10h，然后经过冷压、分切得到正极片。Lithium manganese iron phosphate, binder polyvinylidene fluoride, conductive agent carbon nanotube and conductive agent SP are mixed in a weight ratio of 96.5:2:0.5:1, N-methylpyrrolidone is added, and the mixture is stirred under a vacuum mixer to obtain a positive electrode slurry with a solid content of 65%. The positive electrode slurry is coated on both sides of an aluminum foil, dried at room temperature, and then transferred to an oven at 80°C for drying for 10 hours, and then cold pressed and cut to obtain a positive electrode sheet.
2)负极片的制备2) Preparation of negative electrode
将负极活性材料石墨、负极活性物质硅碳、粘结剂PAA、粘结剂SBR、导电剂CNT和导电剂SP，按照重量比为80:10:3:3:2:2进行混合，加入去离子水，在真空搅拌机下进行搅拌，得到固含量为35％的负极浆料；将负极浆料涂覆于铜箔的两侧，在室温下晾干后转移至80℃烘箱干燥10h，然后经过冷压、分切后得到负极片。The negative electrode active material graphite, the negative electrode active material silicon carbon, the binder PAA, the binder SBR, the conductive agent CNT and the conductive agent SP are mixed in a weight ratio of 80:10:3:3:2:2, deionized water is added, and the mixture is stirred under a vacuum mixer to obtain a negative electrode slurry with a solid content of 35%; the negative electrode slurry is coated on both sides of the copper foil, dried at room temperature, and then transferred to an oven at 80°C for drying for 10 hours, and then cold pressed and cut to obtain a negative electrode sheet.
3)电解质前驱液的制备3) Preparation of electrolyte precursor solution
将4％季戊四醇三丙烯酸酯、3％二乙二醇二甲基丙烯酸酯、0.07％过氧化苯甲酰、25％碳酸丙烯酯(PC)、15％碳酸乙烯酯(EC)、15％碳酸二乙酯(DEC)、24％碳酸甲基乙基酯(EMC)、11.03％氟代碳酸乙烯酯(FEC)、2.9％碳酸亚乙烯酯(VC)，按照质量比均匀混合得到透明液体，往透明液体里面，添加六氟磷酸锂和二氟磷酸锂(9.5:1)，进行溶解，最后达到锂盐浓度为1.45mol/L的电解质前驱液。4% pentaerythritol triacrylate, 3% diethylene glycol dimethacrylate, 0.07% benzoyl peroxide, 25% propylene carbonate (PC), 15% ethylene carbonate (EC), 15% diethyl carbonate (DEC), 24% ethyl methyl carbonate (EMC), 11.03% fluoroethylene carbonate (FEC), and 2.9% vinylene carbonate (VC) are uniformly mixed in a mass ratio to obtain a transparent liquid. Lithium hexafluorophosphate and lithium difluorophosphate (9.5:1) are added into the transparent liquid to dissolve, and finally an electrolyte precursor solution with a lithium salt concentration of 1.45 mol/L is obtained.
4)电池的组装4) Battery assembly
将正极极片、隔膜和负极极片依次层叠并组装得到电芯，将电芯至于外包装中，加入电解质前驱液，经封装、预处理、固化化成、化成等工序后制备得到电池；The positive electrode sheet, the separator and the negative electrode sheet are sequentially stacked and assembled to obtain a battery cell, the battery cell is placed in an outer package, an electrolyte precursor solution is added, and a battery is prepared after packaging, pretreatment, curing, formation and other processes;
其中，所述预处理包括：在55℃的温度下进行预聚反应2h；随后，在80℃的温度、2MPa的压力下，0.15C对预处理后的电池充电至3.7V；在90℃的温度，0.2MPa的压力，0.5C的倍率下将固化化成处理后的电池充电至截止电压4.1V，得到电池。The pretreatment includes: performing a prepolymerization reaction at a temperature of 55°C for 2 hours; then, charging the pretreated battery to 3.7V at 0.15C at a temperature of 80°C and a pressure of 2MPa; charging the cured battery to a cutoff voltage of 4.1V at a temperature of 90°C, a pressure of 0.2MPa, and a rate of 0.5C to obtain a battery.
实施例8Example 8
本实施例提供的电池的制备方法如下：The preparation method of the battery provided in this embodiment is as follows:
1)正极片的制备1) Preparation of positive electrode
将镍钴锰酸锂(镍钴锰6:2:2)、粘结剂聚偏氟乙烯、导电剂碳纳米管和导电剂SP，按照重量比为96.5：2：0.5：1进行混合，加入N-甲基吡咯烷酮，在真空搅拌机下进行搅拌，得到固含量为65％的正极浆料；将正极浆料涂覆于铝箔的两侧，在室温下晾干后转移至80℃烘箱干燥10h，然后经过冷压、分切得到正极片。Lithium nickel cobalt manganese oxide (nickel cobalt manganese 6:2:2), binder polyvinylidene fluoride, conductive agent carbon nanotubes and conductive agent SP are mixed in a weight ratio of 96.5:2:0.5:1, N-methylpyrrolidone is added, and the mixture is stirred under a vacuum mixer to obtain a positive electrode slurry with a solid content of 65%; the positive electrode slurry is coated on both sides of an aluminum foil, dried at room temperature, and then transferred to an oven at 80°C for drying for 10 hours, and then cold pressed and cut to obtain a positive electrode sheet.
2)负极片的制备2) Preparation of negative electrode
将负极活性材料石墨、负极活性物质硅碳、粘结剂PAA、粘结剂SBR、导电剂CNT和导电剂SP，按照重量比为85:5:3:3:2:2进行混合，加入去离子水，在真空搅拌机下进行搅拌，得到固含量为35％的负极浆料；将负极浆料涂覆于铜箔的两侧，在室温下晾干后转移至80℃烘箱干燥10h，然后经过冷压、分切后得到负极片。The negative electrode active material graphite, the negative electrode active material silicon carbon, the binder PAA, the binder SBR, the conductive agent CNT and the conductive agent SP are mixed in a weight ratio of 85:5:3:3:2:2, deionized water is added, and the mixture is stirred under a vacuum mixer to obtain a negative electrode slurry with a solid content of 35%; the negative electrode slurry is coated on both sides of the copper foil, dried at room temperature, and then transferred to an oven at 80°C for drying for 10 hours, and then cold pressed and cut to obtain a negative electrode sheet.
3)电解质前驱液的制备3) Preparation of electrolyte precursor solution
将1％三羟甲基丙烷三甲基丙烯酸酯、3％乙二醇二甲基丙烯酸酯、5％三乙二醇二甲基丙烯酸酯、0.09％过氧化苯甲酸叔丁酯、25％碳酸丙烯酯(PC)、15％碳酸乙烯酯(EC)、15％碳酸二乙酯(DEC)、25％碳酸甲基乙基酯(EMC)、12.05％氟代碳酸乙烯酯(FEC)、2.9％碳酸亚乙烯酯(VC)，按照质量比均匀混合得到透明液体，往透明液体里面，添加六氟磷酸锂和双氟双草酸磷酸锂(7.8:1)，进行溶解，最后达到锂盐浓度为1.45mol/L的电解质前驱液。1% trimethylolpropane trimethacrylate, 3% ethylene glycol dimethacrylate, 5% triethylene glycol dimethacrylate, 0.09% tert-butyl perbenzoate, 25% propylene carbonate (PC), 15% ethylene carbonate (EC), 15% diethyl carbonate (DEC), 25% methyl ethyl carbonate (EMC), 12.05% fluoroethylene carbonate (FEC), and 2.9% vinylene carbonate (VC) are uniformly mixed in a mass ratio to obtain a transparent liquid. Lithium hexafluorophosphate and lithium difluorobisoxalate phosphate (7.8:1) are added into the transparent liquid to dissolve them, and finally an electrolyte precursor solution with a lithium salt concentration of 1.45 mol/L is obtained.
4)电池的组装4) Battery assembly
将正极极片、隔膜和负极极片依次层叠并组装得到电芯，将电芯至于外包装中，加入电解质前驱液，经封装、预处理、固化化成、化成等工序后制备得到电池；The positive electrode sheet, the separator and the negative electrode sheet are sequentially stacked and assembled to obtain a battery cell, the battery cell is placed in an outer package, an electrolyte precursor solution is added, and a battery is prepared after packaging, pretreatment, curing, formation and other processes;
其中，所述预处理包括：在60℃的温度下进行预聚反应1h；随后，在80℃的温度、1.5MPa的压力下，对预处理后的电池充电至3.7V；在90℃的温度，0.2MPa的压力，0.5C的倍率下将固化化成处理后的电池充电至截止电压4.25V，得到电池。The pretreatment includes: performing a prepolymerization reaction at a temperature of 60°C for 1 hour; then, charging the pretreated battery to 3.7V at a temperature of 80°C and a pressure of 1.5MPa; charging the cured battery to a cutoff voltage of 4.25V at a temperature of 90°C, a pressure of 0.2MPa, and a rate of 0.5C to obtain a battery.
对比例1Comparative Example 1
本对比例提供的电池为液体电解质，包括正极极片、负极极片和电解液，正极极片和负极极片参考实施例1，电解液包括26.33％碳酸丙烯酯(PC)、15.8％碳酸乙烯酯(EC)、15.8％碳酸二乙酯(DEC)、26.33％碳酸甲基乙基酯(EMC)、12.69％氟代碳酸乙烯酯(FEC)、3.05％碳酸亚乙烯酯(VC)，按照质量比均匀混合得到透明液体，往透明液体里面，添加六氟磷酸锂和双三氟甲基磺酰亚胺锂(7:1)，进行溶解，最后达到锂盐浓度为1.45mol/L的电解液。The battery provided in this comparative example is a liquid electrolyte, including a positive electrode plate, a negative electrode plate and an electrolyte. The positive electrode plate and the negative electrode plate refer to Example 1. The electrolyte includes 26.33% propylene carbonate (PC), 15.8% ethylene carbonate (EC), 15.8% diethyl carbonate (DEC), 26.33% methyl ethyl carbonate (EMC), 12.69% fluoroethylene carbonate (FEC), and 3.05% vinylene carbonate (VC). They are uniformly mixed in a mass ratio to obtain a transparent liquid. Lithium hexafluorophosphate and lithium bistrifluoromethylsulfonyl imide (7:1) are added to the transparent liquid to dissolve, and finally an electrolyte with a lithium salt concentration of 1.45 mol/L is obtained.
对比例2Comparative Example 2
本实施例提供的电池可参考实施例3，区别在固化和化成阶段。其中，所述预处理包括：在60℃的温度、3MPa的压力下，对预处理后的电池充电至3.7V；在80℃的温度，0.1MPa的压力，0.5C的倍率下将固化化成处理后的电池充电至截止电压4.25V，得到电池。The battery provided in this embodiment can refer to the embodiment 3, and the difference lies in the curing and formation stages. The pretreatment includes: charging the pretreated battery to 3.7V at a temperature of 60°C and a pressure of 3MPa; charging the cured and formed battery to a cut-off voltage of 4.25V at a temperature of 80°C, a pressure of 0.1MPa, and a rate of 0.5C to obtain a battery.
对比例3Comparative Example 3
本实施例提供的电池可参考实施例3，区别在固化和化成阶段。其中，所述预处理包括：在40℃的温度下进行预聚反应2h；随后，在40℃的温度、3MPa的压力下，0.5C对预处理后的电池充电至3.7V；在40℃的温度，0.1MPa的压力，2C的倍率下将固化化成处理后的电池充电至截止电压4.25V，得到电池。The battery provided in this embodiment can refer to Example 3, except for the curing and formation stages. The pretreatment includes: performing a prepolymerization reaction at a temperature of 40°C for 2 hours; then, charging the pretreated battery to 3.7V at 0.5C at a temperature of 40°C and a pressure of 3MPa; charging the cured and formed battery to a cutoff voltage of 4.25V at a temperature of 40°C, a pressure of 0.1MPa, and a rate of 2C to obtain a battery.
试验例Test example
1、热重分析1. Thermogravimetric analysis
对实施例1～8和对比例1～3提供的电池进行拆解，得到电解质，采用去离子水对电解质进行清洗，收集固化组分，100℃烘干24小时后，取固态物质进行热重测试。初始温度为25℃时，测试电解质的质量M0，随后按照5℃/min的升温速率进行升温，在不同温度节点下测试电解质的质量M，最高温度为600℃。热重质量保持率＝100％*(M/M0)，以温度为横坐标，质量保持率为纵坐标，绘制热重分析曲线，实施例1、4～5提供的电解质的热重分析曲线分别如图1-3所示，实施例1～8和对比例1～3提供的电解质的热重数据见表1。The batteries provided in Examples 1 to 8 and Comparative Examples 1 to 3 were disassembled to obtain electrolytes, and the electrolytes were washed with deionized water, and the solidified components were collected. After drying at 100°C for 24 hours, the solid matter was taken for thermogravimetric testing. When the initial temperature was 25°C, the mass M0 of the electrolyte was tested, and then the temperature was increased at a heating rate of 5°C/min, and the mass M of the electrolyte was tested at different temperature nodes, with the highest temperature being 600°C. Thermogravimetric mass retention rate = 100%*(M/M0 ), with temperature as the horizontal axis and mass retention rate as the vertical axis, a thermogravimetric analysis curve was drawn. The thermogravimetric analysis curves of the electrolytes provided in Examples 1 and 4 to 5 are shown in Figures 1-3, respectively, and the thermogravimetric data of the electrolytes provided in Examples 1 to 8 and Comparative Examples 1 to 3 are shown in Table 1.
表1Table 1
2、XRD测试2. XRD test
将以上实施例1～8的电池拆解后，对电解质进行XRD测试，测试角度为10°～90°，根据测试结果，将实施例1～8的电解质的X射线衍射图中出现的衍射峰及其半峰宽在以下中列出。After disassembling the batteries of the above Examples 1 to 8, the electrolytes were subjected to XRD testing at a testing angle of 10° to 90°. Based on the test results, the diffraction peaks and their half-peak widths appearing in the X-ray diffraction patterns of the electrolytes of Examples 1 to 8 are listed below.
表2Table 2
3、炉温测试条件3. Furnace temperature test conditions
对实施例1～8和对比例1～3提供的电池在25℃±5℃、0.2C放电至下限电压，静置10min，以0.5C充电至上限电压，截止0.05C，静置10min，并测试电池满电状态下的电压；将电池置于热冲击试验箱中，以5℃±2℃/min的速度升至200℃，不同时间下监控电池温度，实施例1～3和对比例1～2提供的电池的炉温测试图分别如图4～8所示，实施例1～8和对比例1～3的测试结果见表3。The batteries provided in Examples 1 to 8 and Comparative Examples 1 to 3 were discharged to the lower limit voltage at 25°C ± 5°C and 0.2C, left to stand for 10 min, charged to the upper limit voltage at 0.5C, cut off at 0.05C, left to stand for 10 min, and the voltage of the battery in the fully charged state was tested; the battery was placed in a thermal shock test box, the temperature was raised to 200°C at a rate of 5°C ± 2°C/min, and the battery temperature was monitored at different times. The furnace temperature test diagrams of the batteries provided in Examples 1 to 3 and Comparative Examples 1 to 2 are shown in Figures 4 to 8, respectively, and the test results of Examples 1 to 8 and Comparative Examples 1 to 3 are shown in Table 3.
表3Table 3
4、电池循环测试条件4. Battery cycle test conditions
对实施例1～8和对比例1～3提供的电池在25℃、0.2C放电至下限电压，静置10min，以0.5C充放电至上限电压，截止0.05C，收集电池循环1000次容量保持率信息。以初次循环容量为A0，电池循环X次，测试容量为Ax，电池循环X次容量保持率为100％*(Ax/A0)，测试结果见表4。The batteries provided in Examples 1 to 8 and Comparative Examples 1 to 3 were discharged to the lower voltage limit at 25°C and 0.2C, left to stand for 10 minutes, charged and discharged to the upper voltage limit at 0.5C, cut off at 0.05C, and the capacity retention rate information of the battery after 1000 cycles was collected. The initial cycle capacity is A0 , the battery is cycled X times, the test capacity is Ax , and the capacity retention rate of the battery after X cycles is 100%*(Ax /A0 ). The test results are shown in Table 4.
表4Table 4
根据表1～4提供的数据可知，本申请提供的电解质具有较好的热稳定性，能够有效延长电池的ARC热失控时间，提高电池的安全性，改善电池的循环性能。According to the data provided in Tables 1 to 4, the electrolyte provided in the present application has good thermal stability, can effectively prolong the ARC thermal runaway time of the battery, improve the safety of the battery, and improve the cycle performance of the battery.
最后应说明的是：以上各实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述各实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2023/105426WO2025000557A1 (en) | 2023-06-30 | 2023-06-30 | Battery and electronic device |
| CN202380014342.6ACN119547242A (en) | 2023-06-30 | 2023-06-30 | Battery and electronic equipment |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2023/105426WO2025000557A1 (en) | 2023-06-30 | 2023-06-30 | Battery and electronic device |
| Publication Number | Publication Date |
|---|---|
| WO2025000557A1true WO2025000557A1 (en) | 2025-01-02 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2023/105426PendingWO2025000557A1 (en) | 2023-06-30 | 2023-06-30 | Battery and electronic device |
| Country | Link |
|---|---|
| CN (1) | CN119547242A (en) |
| WO (1) | WO2025000557A1 (en) |
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|---|---|---|---|---|
| JP2005194304A (en)* | 2003-12-26 | 2005-07-21 | Uni-Chemical Co Ltd | Phosphate group-containing hydrocarbon oligomer material and / or phosphate group-containing hydrocarbon polymer material, and composite solid electrolyte membrane containing acidic group-containing fullerene derivative and use thereof |
| US20120077092A1 (en)* | 2010-09-27 | 2012-03-29 | Samsung Electronics Co., Ltd. | Electrolyte membrane for lithium battery, lithium battery using the electrolyte membrane, and method of preparing the electrolyte membrane |
| CN104098785A (en)* | 2013-04-07 | 2014-10-15 | 中国科学院长春应用化学研究所 | Pvdf gel polymer electrolyte and preparation method thereof |
| CN106532116A (en)* | 2016-12-19 | 2017-03-22 | 中国科学院化学研究所 | Preparation method and application of high-temperature resistant solid-state polymer electrolyte |
| CN110679028A (en)* | 2017-05-24 | 2020-01-10 | 出光兴产株式会社 | Sulfide solid electrolyte |
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005194304A (en)* | 2003-12-26 | 2005-07-21 | Uni-Chemical Co Ltd | Phosphate group-containing hydrocarbon oligomer material and / or phosphate group-containing hydrocarbon polymer material, and composite solid electrolyte membrane containing acidic group-containing fullerene derivative and use thereof |
| US20120077092A1 (en)* | 2010-09-27 | 2012-03-29 | Samsung Electronics Co., Ltd. | Electrolyte membrane for lithium battery, lithium battery using the electrolyte membrane, and method of preparing the electrolyte membrane |
| CN104098785A (en)* | 2013-04-07 | 2014-10-15 | 中国科学院长春应用化学研究所 | Pvdf gel polymer electrolyte and preparation method thereof |
| CN106532116A (en)* | 2016-12-19 | 2017-03-22 | 中国科学院化学研究所 | Preparation method and application of high-temperature resistant solid-state polymer electrolyte |
| CN110679028A (en)* | 2017-05-24 | 2020-01-10 | 出光兴产株式会社 | Sulfide solid electrolyte |
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| CN119547242A (en) | 2025-02-28 |
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