技术领域technical field
本发明涉及一种电池化成方法，特别涉及一种锂离子二次电池化成方法。The invention relates to a battery formation method, in particular to a lithium ion secondary battery formation method.
背景技术Background technique
锂离子电池是一种新型的化学电源，因其具有能量密度大、工作电压高、寿命长、环保的特点，广泛应用于移动电话等便携式电子产品中。Lithium-ion battery is a new type of chemical power source, which is widely used in portable electronic products such as mobile phones because of its high energy density, high operating voltage, long life, and environmental protection.
化成是指对电池进行首次充放电的过程。锂离子二次充电电池的化成步骤是制造电池的重要阶段，化成关系到电池的容量高低、自放电性能等多方面的品质。Formation refers to the process of charging and discharging the battery for the first time. The formation step of lithium-ion rechargeable batteries is an important stage in the manufacture of batteries. The formation is related to the quality of the battery's capacity and self-discharge performance.
目前锂离子二次充电电池采用的化成方法是：先以0.01C-1C的电流进行小电流恒流充电，再以0.05C-10C的大电流恒流充电，然后在30-80℃陈化0.5-160小时。通过该方法化成的锂离子二次电池在储存的时候自放电现象严重，低电压电池比率大的问题，严重影响锂离子二次电池的性能，还造成能源的浪费。At present, the formation method used in lithium-ion secondary rechargeable batteries is: first charge with a small current and a constant current at a current of 0.01C-1C, then charge with a large current and a constant current of 0.05C-10C, and then age at 30-80°C for 0.5 -160 hours. The lithium-ion secondary battery formed by this method has a serious self-discharge phenomenon during storage, and the problem of a large ratio of low-voltage batteries seriously affects the performance of the lithium-ion secondary battery and causes waste of energy.
发明内容Contents of the invention
本发明所要解决的问题是：现有化成方法中生产的电池自放电现象严重，电池低电压比率高。The problem to be solved by the invention is: the self-discharge phenomenon of the battery produced in the existing chemical formation method is serious, and the low voltage ratio of the battery is high.
本发明的发明人意外的发现：造成电池自放电现象严重的根本原因是金属杂质引发的锂枝晶所导致的，由于电芯正极中的金属杂质(主要为Fe和Ni)会在首次充电过程中聚集到负极表面，以大晶粒形态呈现，采用现有技术的化成方法，大晶粒的金属杂质会堵塞在石墨层间空隙，造成Li+无法嵌入，从而Li+堆叠在金属单质上形成锂枝晶，容易诱发电池内部微短路，造成锂电池自放电严重，低电压电池比率大。The inventors of the present invention have unexpectedly found that the root cause of the serious battery self-discharge phenomenon is the lithium dendrites caused by metal impurities, because the metal impurities (mainly Fe and Ni) in the positive electrode of the battery will In the form of large grains, metal impurities with large grains will block the gaps between the graphite layers, resulting in the inability of Li+ to be embedded, so that Li+ stacks on the metal element to form Lithium dendrites can easily induce micro-short circuits inside the battery, resulting in serious self-discharge of the lithium battery, and a large ratio of low-voltage batteries.
本发明提供了一种锂离子二次电池的化成方法，该方法在化成温度下对电池进行化成，第一阶段以恒流充电至V2伏特，然后在V2-V1伏特循环恒流充放电至少1次，第二阶段以恒流充电至V3伏特，电压V1<电压V2<电压V3。The invention provides a method for forming a lithium ion secondary battery. In the method, the battery is formed at the formation temperature. In the first stage, the battery is charged to V2 volts at a constant current, and then the constant current is charged at V2 -V1 volt cycle. Discharge at least once, and charge to V3 volts with constant current in the second stage, voltage V1 < voltage V2 < voltage V3 .
本发明提供的方法，以恒流充电至V2伏特，然后在V2-V1伏特循环充放电至少1次，可以使金属杂质Fe和Ni在正负极上往返运动，打散其在首次充电中形成的大晶粒，变成更多的小颗粒散布在负极表面，这样即使Li+无法嵌入到石墨层内而堆叠在金属单质上，也会因为颗粒直径较小而不会形成能影响电池微短路的锂枝晶。The method provided by the present invention charges to V2 volts with a constant current, and then charges and discharges at least once at V2 -V1 volt cycle, which can make the metal impurities Fe and Ni move back and forth on the positive and negative electrodes, and break them up for the first time. The large crystal grains formed during charging become more small particles scattered on the surface of the negative electrode, so that even if Li+ cannot be embedded in the graphite layer and stacked on the metal element, it will not form due to the small diameter of the particles. Micro-short-circuited lithium dendrites in batteries.
本发明的有益效果是：本发明可以有效抑制电池自放电现象，降低低电压电池比率，避免能源浪费。The beneficial effects of the invention are: the invention can effectively suppress the battery self-discharge phenomenon, reduce the ratio of low-voltage batteries, and avoid energy waste.
具体实施方式Detailed ways
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer, the present invention will be further described in detail below in conjunction with the embodiments.
一种锂离子二次电池的化成方法，该方法在化成温度下对电池进行化成，第一阶段以恒流充电至V2伏特，然后在V2-V1伏特循环恒流充放电至少1次，第二阶段以恒流充电至V3伏特，电压V1<电压V2<电压V3。A method for forming a lithium-ion secondary battery, the method is to form the battery at the formation temperature, charge at a constant current to V2 volts in the first stage, and then charge and discharge at a constant current at V2 -V1 volts for at least one time , the second stage is charged to V3 volts with constant current, voltage V1 < voltage V2 < voltage V3 .
所述化成温度为本领域技术人员所公知的，本发明电池的化成温度优选为20-40℃。The formation temperature is well known to those skilled in the art, and the formation temperature of the battery of the present invention is preferably 20-40°C.
所述V2-V1伏特循环恒流充放电是指从V2伏特以恒流放电至V1伏特，再从V1伏特以恒流充电V2伏特为一次V2-V1伏特循环恒流充放电。The V2 -V1 volt cycle constant current charge and discharge refers to discharging from V2 volts to V1 volts with a constant current, and then charging V2 volts with a constant current from V1 volts is a V2 -V1 volt cycle constant Flow charge and discharge.
其中，电压V1优选为2.3-2.5V，更优选为2.45-2.5V；电压V2优选为3.5-3.7V，更优选为3.5-3.55V；电压V3优选为3.85-4.0V，更优选为3.85-3.95V。Among them, the voltage V1 is preferably 2.3-2.5V, more preferably 2.45-2.5V; the voltage V2 is preferably 3.5-3.7V, more preferably 3.5-3.55V; the voltage V3 is preferably 3.85-4.0V, more preferably 3.85-3.95V.
其中，恒流充电电流为0.01-0.1C，优选第一阶段恒流充电电流为0.02-0.05C，第二阶段恒流充电电流为0.08C-0.1C；Among them, the constant-current charging current is 0.01-0.1C, preferably the first-stage constant-current charging current is 0.02-0.05C, and the second-stage constant-current charging current is 0.08C-0.1C;
其中，放电电流为0.01-0.1C，优选为0.03-0.08C。Wherein, the discharge current is 0.01-0.1C, preferably 0.03-0.08C.
其中，在V2-V1伏特循环充放电的次数优选为2-10次，进一步优选为，在V2-V1伏特循环充放电的次数为2-5次。Wherein, the number of charging and discharging cycles at V2 -V1 volts is preferably 2-10 times, and more preferably, the number of charging and discharging cycles at V2 -V1 volts is 2-5 times.
本发明人发现，循环充放电的次数在10次以内，每次循环充放电对于电池化成的效果增加非常显著，同时化成时间较短。The present inventors found that the charging and discharging cycles are less than 10 times, and the effect of each charge and discharge cycle on battery formation is significantly increased, and the formation time is relatively short.
该化成方法优选在第一阶段以恒流充电至V2伏特之后，将电池放置，放置时间一般为2-15分钟。还可以优选在第一阶段完成之后，第二阶段之前，将电池陈化，一般陈化3天。In the formation method, the battery is preferably placed after being charged to V2 volts with a constant current in the first stage, and the standing time is generally 2-15 minutes. It is also preferable to age the battery after the completion of the first stage and before the second stage, generally for 3 days.
该化成方法对电池进行化成的设备为本领域技术人员所公知，一般来说，在向密封有极芯的电池壳体内注入电解液之后，用胶纸将注液孔封住，然后将电池放置在充电装置的卡具上，充电装置的正极卡具对应锂离子电池的正极，充电装置的负极卡具对应锂离子电池的负极，设置好充电电流后对电池进行化成，化成完成后密封注液孔。The chemical formation method for the battery is well known to those skilled in the art. Generally speaking, after injecting the electrolyte into the battery casing sealed with the pole core, seal the liquid injection hole with adhesive tape, and then place the battery On the fixture of the charging device, the positive pole fixture of the charging device corresponds to the positive pole of the lithium-ion battery, and the negative pole fixture of the charging device corresponds to the negative pole of the lithium-ion battery. After the charging current is set, the battery is formed, and the liquid is injected after the formation is completed. hole.
下面将通过实施例对本发明作进一步地具体说明。The present invention will be further specifically described below by way of examples.
实施例1Example 1
取1万只正常生产的注液后电池LP463446ARU，用0.03C电流充电至3.4V后，放置5分钟后以0.05C的放电电流和0.03C的充电电流在3.4V-2.3V循环充放电4次，充电电流0.03C，放电电流0.05C，并密封注液孔。陈化3天后继续用0.1C将电池恒流充电到4.1V后完成化成，得到化成后的锂离子电池A1。Take 10,000 normally produced batteries LP463446ARU after liquid injection, charge them to 3.4V with a current of 0.03C, and then charge and discharge them 4 times at 3.4V-2.3V with a discharge current of 0.05C and a charge current of 0.03C after standing for 5 minutes. , The charging current is 0.03C, the discharging current is 0.05C, and the injection hole is sealed. After aging for 3 days, continue to charge the battery at a constant current of 0.1C to 4.1V, and then complete the formation to obtain the formed lithium-ion battery A1.
实施例2Example 2
取1万只正常生产的注液后电池LP463446ARU，用0.03C电流充电至3.5V后，放置5分钟后以0.05C的放电电流和0.03C的充电电流在3.5V-2.3V循环充放电2次，充电电流0.03C，放电电流0.05C，并密封注液孔。陈化3天后继续用0.1C将电池恒流充电到3.85V后完成化成，得到化成后的锂离子电池A2。Take 10,000 normally produced batteries LP463446ARU after liquid injection, charge them to 3.5V with a current of 0.03C, and then charge and discharge twice at 3.5V-2.3V with a discharge current of 0.05C and a charge current of 0.03C after standing for 5 minutes , The charging current is 0.03C, the discharging current is 0.05C, and the injection hole is sealed. After aging for 3 days, continue to charge the battery at a constant current of 0.1C to 3.85V, and then complete the formation to obtain the formed lithium-ion battery A2.
实施例3Example 3
取1百万只正常生产的注液后电池LP463446ARU，用0.05C电流充电至3.7V，搁置5分钟后以0.08C的放电电流和0.05C的充电电流在3.5V-2.3V循环充放电2次。继续用0.05C电流恒流充电至3.7V，并密封注液孔。陈化3天后继续用0.1C将电池恒流充电到4.0V后完成化成，得到化成后的锂离子电池A3。Take 1,000,000 LP463446ARU batteries after liquid injection in normal production, charge them to 3.7V with a current of 0.05C, and then cycle charge and discharge twice at 3.5V-2.3V with a discharge current of 0.08C and a charge current of 0.05C for 5 minutes . Continue to charge with a constant current of 0.05C to 3.7V, and seal the liquid injection hole. After aging for 3 days, continue to charge the battery at a constant current of 0.1C to 4.0V and then complete the formation to obtain the formed lithium ion battery A3.
实施例4Example 4
取1百万只正常生产的注液后电池LP463446ARU，用0.04C电流充电至3.53V，搁置5分钟后以0.05C的放电电流和0.04C的充电电流在3.5V-2.3V循环充放电2次。继续用0.04C电流恒流充电至3.55V，并密封注液孔。陈化3天后继续用0.09C将电池恒流充电到3.95V后完成化成，得到化成后的锂离子电池A4。Take 1,000,000 LP463446ARU batteries after liquid injection in normal production, charge them to 3.53V with a current of 0.04C, and then cycle charge and discharge twice at 3.5V-2.3V with a discharge current of 0.05C and a charge current of 0.04C for 5 minutes . Continue to charge with a constant current of 0.04C to 3.55V, and seal the liquid injection hole. After aging for 3 days, continue to charge the battery at a constant current of 0.09C to 3.95V, and then complete the formation to obtain the formed lithium-ion battery A4.
比较例comparative example
取1百万只正常生产的注液后电池LP463446ARU，用0.05C电流直接充电至3.7V后密封注液孔，不再进行循环。陈化3天后继续用0.1C将电池恒流充电到3.85V后完成化成，得到化成后的锂离子电池D1。Take 1 million LP463446ARU batteries after liquid injection in normal production, charge them directly to 3.7V with a current of 0.05C, seal the liquid injection hole, and no longer cycle. After aging for 3 days, continue to charge the battery at a constant current of 0.1C to 3.85V, and then complete the formation to obtain the formed lithium-ion battery D1.
低电压比率测试Low Voltage Ratio Test
将实施例1-3和比较例1得到的化成后的锂离子电池A1-A3和D1，在常温下直接恒压充电至4.2V，充电截至电流20mA。然后以0.5C放电至3.0V，最后将电池用0.3C恒流恒压至3.82-3.86V，储存30天，电压低于3.0V的电池占电池总数的比率定义为低电压比率，结果如表1所示。The formed lithium-ion batteries A1-A3 and D1 obtained in Examples 1-3 and Comparative Example 1 were directly charged at a constant voltage to 4.2V at room temperature, and the charging cut-off current was 20mA. Then discharge it at 0.5C to 3.0V, and finally use 0.3C constant current and constant voltage to 3.82-3.86V, store for 30 days, the ratio of the battery whose voltage is lower than 3.0V to the total number of batteries is defined as the low voltage ratio, and the results are shown in the table 1.
初始容量测试initial capacity test
将实施例1-3和比较例1得到的化成后的锂离子电池A1-A3和D1，在常温下直接恒压充电至4.2V，充电截至电流20mA。然后以0.5C放电至3.0V，测定得到电池放电的初始容量，结果如表2所示。The formed lithium-ion batteries A1-A3 and D1 obtained in Examples 1-3 and Comparative Example 1 were directly charged at a constant voltage to 4.2V at room temperature, and the charging cut-off current was 20mA. Then it was discharged to 3.0V at 0.5C, and the initial discharge capacity of the battery was measured. The results are shown in Table 2.
表1储存30天后低电压比率Table 1 Low voltage ratio after storage for 30 days
从表1可以看出，实施例的电池A1-A3的低电压比率均处于1600ppm之下，也就是在1百万电池在储存30天后只有少于1600只电池的电压小于3.0V，而对比例1的电池有5733只的电压小于3.0V。对比例的低电压比率是实施例1-3的三倍多。由此可见，本发明有效抑制电池自放电现象严重的问题。As can be seen from Table 1, the low voltage ratios of the batteries A1-A3 of the embodiment are all below 1600ppm, that is, the voltage of less than 1600 batteries is less than 3.0V after 1 million batteries are stored for 30 days, while the comparative example 1 of the batteries has 5733 voltages less than 3.0V. The low voltage ratio of the comparative example is more than three times that of Examples 1-3. It can be seen that the present invention effectively suppresses the serious problem of battery self-discharge.
表2电池放电的初始容量分布比率(电池的设计容量为800mAh)Table 2 The initial capacity distribution ratio of battery discharge (the design capacity of the battery is 800mAh)
从表2可以看出，实施例A1-A3和对比例D1的产品初始容量分布基本相同。可见本发明的方法几乎没有造成电池活性材料不可逆转的浪费，对电池容量基本没有影响。It can be seen from Table 2 that the initial capacity distributions of the products of Examples A1-A3 and Comparative Example D1 are basically the same. It can be seen that the method of the present invention hardly causes irreversible waste of battery active materials, and basically has no impact on battery capacity.
综上所述，可见本发明可以有效抑制电池在储存过程中的自放电现象，降低低电压电池比率，避免能源浪费。同时并不影响电池的初始容量比率分布，依然保持高容量分布。In summary, it can be seen that the present invention can effectively suppress the self-discharge phenomenon of the battery during storage, reduce the ratio of low-voltage batteries, and avoid energy waste. At the same time, it does not affect the initial capacity ratio distribution of the battery, and still maintains a high capacity distribution.
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| CN2008102166773ACN101714665B (en) | 2008-10-07 | 2008-10-07 | Battery formation method |
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