技术领域technical field
本发明属于锂离子二次电池技术领域，尤其涉及一种锂离子二次电池的首次充电化成方法。The invention belongs to the technical field of lithium-ion secondary batteries, and in particular relates to a first-time charging formation method of lithium-ion secondary batteries.
背景技术Background technique
目前，锂离子二次电池的首次充电化成方法是以一定的电流恒流对电池进行充电至3.4V～3.9V，然后对电池进行抽真空封口，封口后再老化24h～168h，最后恒流充电至4.2V。这种方法的弊端在于：形成固体电解质界面膜（SEI膜）的过程中，会伴随一定的副反应发生，产生有害气体。有害气体不能在形成固体电解质界面膜的过程中及时排出，而是存在于极片和隔膜之间，当电压到达3.4V～3.9V后在低压环境内贮存时气体才能逸出。因此在抽真空之前有害气体以杂质的方式存在于电池的内部，影响电池的尺寸、内阻和倍率等，甚至会继续干扰、破坏电池的充放电反应。经封口老化的3.4V～3.9V的电池以恒流（分为大电流（倍率为0.5C～2C）和小电流（倍率为0.1C～0.5C）两种方式）的方式进行充电至4.2V。这种充电方式的弊端在于：小电流充电会延长电池的生产周期，大电流充电尤其是高电压段时的大电流充电则会造成负极析锂，进而影响电池的容量、寿命和安全等各种性能。因此单纯的采用小电流或大电流都存在明显的不足。At present, the first charging formation method of lithium-ion secondary batteries is to charge the battery with a certain current and constant current to 3.4V ~ 3.9V, then vacuumize and seal the battery, and then aging for 24h ~ 168h after sealing, and finally charge with constant current to 4.2V. The disadvantage of this method is that in the process of forming the solid electrolyte interface film (SEI film), certain side reactions will occur and harmful gases will be generated. The harmful gas cannot be discharged in time during the formation of the solid electrolyte interface film, but exists between the pole piece and the diaphragm. When the voltage reaches 3.4V ~ 3.9V, the gas can escape when it is stored in a low-pressure environment. Therefore, harmful gases exist inside the battery in the form of impurities before vacuuming, affecting the size, internal resistance and rate of the battery, and even continue to interfere and destroy the charge and discharge reaction of the battery. The sealed and aged 3.4V～3.9V battery is charged to 4.2V by constant current (divided into two methods: high current (0.5C～2C) and low current (0.1C～0.5C)) . The disadvantage of this charging method is that charging with a small current will prolong the production cycle of the battery, and charging with a large current, especially at a high voltage range, will cause lithium to be deposited on the negative electrode, which will affect the capacity, life and safety of the battery. performance. Therefore, there are obvious deficiencies in simply adopting small current or large current.
有鉴于此，确有必要提供一种锂离子二次电池的首次充电化成方法，该方法通过改进锂离子二次电池的首次充电化成的工艺和参数等，有效地克服了现有技术中的首次充电化成方法导致的有害气体产生后残留在锂离子二次电池内部的问题，更好的保证Li+的迁移，使形成的SEI膜更加均一、稳定和致密，从而保证锂离子二次电池的容量、寿命、内阻、倍率和安全等性能，提高产品的质量。此外，采用本发明还能缩短电池的生产周期。In view of this, it is necessary to provide a method for the formation of the first charge of lithium-ion secondary batteries, which effectively overcomes the first-time problems in the prior art by improving the process and parameters of the formation of lithium-ion secondary batteries for the first time. The problem of harmful gas caused by the charge formation method remaining inside the lithium-ion secondary battery can better ensure the migration of Li+ , making the formed SEI film more uniform, stable and dense, thereby ensuring the capacity of the lithium-ion secondary battery , life, internal resistance, magnification and safety and other properties to improve product quality. In addition, the production cycle of batteries can be shortened by adopting the invention.
发明内容Contents of the invention
本发明的目的在于：针对现有技术的不足，而提供一种锂离子二次电池的首次充电化成方法，该方法通过改进锂离子二次电池的首次充电化成的工艺和参数等，有效地克服了现有技术中的首次充电化成方法导致的有害气体产生后残留在锂离子二次电池内部的问题，更好的保证Li+的迁移，使形成的SEI膜更加均一、稳定和致密，从而保证锂离子二次电池的容量、寿命、内阻、倍率和安全等性能，提高产品的质量。此外，采用本发明还能缩短电池的生产周期。The object of the present invention is: aim at the deficiencies in the prior art, and provide a kind of lithium-ion secondary battery charging and forming method for the first time, this method overcomes effectively by improving the process and parameters etc. It solves the problem of harmful gas remaining inside the lithium-ion secondary battery after the first charge formation method in the prior art, better ensures the migration of Li+ , and makes the formed SEI film more uniform, stable and dense, thereby ensuring The capacity, life, internal resistance, rate and safety of lithium-ion secondary batteries improve product quality. In addition, the production cycle of batteries can be shortened by adopting the invention.
为了达到上述目的，本发明采用如下技术方案，一种锂离子二次电池的首次充电化成方法，包括以下步骤：第一步，将已注有电解液的锂离子二次电池在温度为20℃～70℃和相对湿度小于或等于10%的环境下陈化处理2～96h，然后在负压状态下逐步增加充电电流对电池进行分段充电化成，当电压到达3.6V时，对电池进行封口。In order to achieve the above object, the present invention adopts the following technical scheme, a method for forming a lithium-ion secondary battery for the first charge, comprising the following steps: in the first step, the lithium-ion secondary battery that has been injected with electrolyte is heated at a temperature of 20°C Aging treatment at ~70°C and relative humidity less than or equal to 10% for 2 to 96 hours, then gradually increase the charging current under negative pressure to charge and form the battery in stages, and seal the battery when the voltage reaches 3.6V .
第二步，对封口后的电池进行2h～480h的老化处理，然后先以0.5C～1C的倍率恒流充电至3.8～4.0V，再以0.2C～0.5C的倍率恒流充电至4.2V，最后在4.2V下恒压充电，充电截止电流为10mA～200mA。The second step is to perform aging treatment on the sealed battery for 2h~480h, and then charge it to 3.8~4.0V with a constant current rate of 0.5C~1C, and then charge it to 4.2V with a constant current rate of 0.2C~0.5C , and finally charged at a constant voltage of 4.2V, the charging cut-off current is 10mA ~ 200mA.
作为本发明锂离子二次电池的首次充电化成方法的一种改进，所述负压为-0.01MPa～-0.099MPa。As an improvement to the formation method of the lithium ion secondary battery for the first charge of the present invention, the negative pressure is -0.01MPa˜-0.099MPa.
作为本发明锂离子二次电池的首次充电化成方法的一种改进，所述负压为-0.085MPa～-0.092MPa。As an improvement to the formation method of the first charge of the lithium ion secondary battery of the present invention, the negative pressure is -0.085MPa˜-0.092MPa.
作为本发明锂离子二次电池的首次充电化成方法的一种改进，第一步所述充电化成为先以0.01C～0.03C的倍率恒流充电至2.5V，再以0.05C～0.1C的倍率恒流充电至3.2V，然后以0.1C～0.2C的倍率恒流充电至3.6V。As an improvement of the first charge formation method of the lithium ion secondary battery of the present invention, the charge formation described in the first step is first charged to 2.5V with a constant current at a rate of 0.01C to 0.03C, and then charged at a rate of 0.05C to 0.1C. Charge to 3.2V with constant current, and then charge to 3.6V with constant current at a rate of 0.1C to 0.2C.
作为本发明锂离子二次电池的首次充电化成方法的一种改进，第一步所述充电化成为先以0.01C的倍率恒流充电至2.5V，再以0.05C的倍率恒流充电至3.2V，然后以0.1C的倍率恒流充电至3.6V。As an improvement of the first charge formation method of the lithium-ion secondary battery of the present invention, the charge formation described in the first step is first charged to 2.5V with a constant current rate of 0.01C, and then charged to 3.2V with a constant current rate of 0.05C. V, and then charged to 3.6V with a constant current at a rate of 0.1C.
作为本发明锂离子二次电池的首次充电化成方法的一种改进，所述陈化处理的温度为20℃～40℃，这是较佳的选择。As an improvement to the formation method for the first charge of the lithium-ion secondary battery of the present invention, the temperature of the aging treatment is 20° C. to 40° C., which is a better choice.
作为本发明锂离子二次电池的首次充电化成方法的一种改进，所述陈化处理的持续时间为12h～24h，这是较佳的选择。As an improvement to the formation method of the first charge of the lithium ion secondary battery of the present invention, the duration of the aging treatment is 12h-24h, which is a better choice.
作为本发明锂离子二次电池的首次充电化成方法的一种改进，所述老化处理的持续时间为24h～72h，这是较佳的选择。As an improvement to the formation method of the first charge of the lithium-ion secondary battery of the present invention, the duration of the aging treatment is 24h-72h, which is a better choice.
作为本发明锂离子二次电池的首次充电化成方法的一种改进，所述老化处理的温度为10℃～70℃。As an improvement of the formation method for the first charge of the lithium-ion secondary battery of the present invention, the temperature of the aging treatment is 10°C to 70°C.
作为本发明锂离子二次电池的首次充电化成方法的一种改进，第二步老化处理后，先以0.5C的倍率恒流充电至4.0V，再以0.2C的倍率恒流充电至4.2V，最后在4.2V下恒压充电，充电截止电流为10mA～200mA。As an improvement of the first charging formation method of the lithium-ion secondary battery of the present invention, after the second step of aging treatment, it is charged to 4.0V with a constant current rate of 0.5C, and then charged to 4.2V with a constant current rate of 0.2C. , and finally charged at a constant voltage of 4.2V, the charging cut-off current is 10mA ~ 200mA.
相对于现有技术，首先，本发明采用分段充电化成的方法先将电池充电至3.6V，可以将在形成固体电解质界面膜（SEI膜）的过程中产生的有害气体及时排出，更好的保证Li+的迁移，使形成的SEI膜更加均一、稳定和致密，从而有效地避免有害气体对电池的尺寸、内阻和倍率及充放电反应造成的不良影响，提高其循环性能和大倍率放电性能。其次，在电池老化后，先以大电流充电、再以小电流充电，充分结合了大电流充电和小电流充电的优点，避开了二者的缺点，不仅可以缩短电池的生产周期，也可以避免负极析锂问题的发生，从而保证电池的循环寿命和安全性能等各种性能。Compared with the prior art, firstly, the present invention adopts the method of segmented charge formation to charge the battery to 3.6V, which can discharge the harmful gas generated in the process of forming the solid electrolyte interfacial film (SEI film) in time, and better Ensure the migration of Li+ , so that the formed SEI film is more uniform, stable and dense, so as to effectively avoid the adverse effects of harmful gases on the size, internal resistance, rate and charge-discharge reaction of the battery, and improve its cycle performance and large-rate discharge performance. Secondly, after the battery ages, it is first charged with a large current, and then charged with a low current, which fully combines the advantages of high current charging and low current charging, and avoids the shortcomings of the two. It can not only shorten the production cycle of the battery, but also Avoid the occurrence of the problem of lithium precipitation at the negative electrode, thereby ensuring various performances such as the cycle life and safety performance of the battery.
具体实施方式Detailed ways
下面结合具体实施例对本发明及其有益效果进行详细的说明，但是本发明的具体实施方式并不仅限于此。The present invention and its beneficial effects will be described in detail below in conjunction with specific examples, but the specific implementation of the present invention is not limited thereto.
实施例1，本实施例提供的一种锂离子二次电池的首次充电化成方法，包括以下步骤：第一步，将已注有电解液的锂离子二次电池在温度为20℃和相对湿度小于或等于10%的环境下陈化处理12h，然后在-0.085MPa的负压状态下，先以0.01C的倍率恒流充电至2.5V，再以0.05C的倍率恒流充电至3.2V，然后以0.1C的倍率恒流充电至3.6V，当电压到达3.6V时，对电池进行封口。Embodiment 1, a kind of lithium ion secondary battery that this embodiment provides the initial charge formation method, comprises the following steps: the first step, the lithium ion secondary battery that has been filled with electrolyte is heated at a temperature of 20°C and relative humidity Aged for 12 hours in an environment less than or equal to 10%, and then charged to 2.5V with a constant current rate of 0.01C at a negative pressure of -0.085MPa, and then charged to 3.2V with a constant current rate of 0.05C. Then charge to 3.6V with a constant current at a rate of 0.1C, and seal the battery when the voltage reaches 3.6V.
第二步，对封口后的电池在50℃下进行24h的老化处理，然后先以0.5C的倍率恒流充电至4.0V，再以0.2C的倍率恒流充电至4.2V，最后在4.2V下恒压充电，充电截止电流为100mA。In the second step, the sealed battery is aged at 50°C for 24 hours, then charged to 4.0V with a constant current rate of 0.5C, then charged to 4.2V with a rate of 0.2C, and finally charged at 4.2V Under constant voltage charging, the charging cut-off current is 100mA.
实施例2，本实施例提供的一种锂离子二次电池的首次充电化成方法，包括以下步骤：第一步，将已注有电解液的锂离子二次电池在温度为70℃和相对湿度小于或等于10%的环境下陈化处理24h，然后在-0.092MPa的负压状态下，先以0.02C的倍率恒流充电至2.5V，再以0.07C的倍率恒流充电至3.2V，然后以0.15C的倍率恒流充电至3.6V，当电压到达3.6V时，对电池进行封口。Embodiment 2, a method for forming a lithium-ion secondary battery for the first time provided by this embodiment, comprises the following steps: the first step, the lithium-ion secondary battery that has been injected with electrolyte is heated at a temperature of 70°C and a relative humidity Aged for 24 hours in an environment less than or equal to 10%, and then charged at a rate of 0.02C to 2.5V at a constant current rate of 0.02C, and then charged to 3.2V at a rate of 0.07C under a negative pressure of -0.092MPa. Then charge it to 3.6V with a constant current at a rate of 0.15C, and seal the battery when the voltage reaches 3.6V.
第二步，对封口后的电池在70℃下进行72h的老化处理，然后先以0.7C的倍率恒流充电至3.9V，再以0.3C的倍率恒流充电至4.2V，最后在4.2V下恒压充电，充电截止电流为10mA。In the second step, the sealed battery is aged at 70°C for 72 hours, then charged to 3.9V with a constant current rate of 0.7C, then charged to 4.2V with a rate of 0.3C, and finally charged at 4.2V Under constant voltage charging, the charging cut-off current is 10mA.
实施例3，本实施例提供的一种锂离子二次电池的首次充电化成方法，包括以下步骤：第一步，将已注有电解液的锂离子二次电池在温度为50℃和相对湿度小于或等于3%的环境下陈化处理18h，然后在-0.090MPa的负压状态下，先以0.03C的倍率恒流充电至2.5V，再以0.1C的倍率恒流充电至3.2V，然后以0.2C的倍率恒流充电至3.6V，当电压到达3.6V时，对电池进行封口。Embodiment 3, a method for forming a lithium-ion secondary battery for the first time provided in this embodiment, comprises the following steps: the first step, the lithium-ion secondary battery that has been injected with electrolyte is heated at a temperature of 50°C and a relative humidity Aged for 18 hours in an environment less than or equal to 3%, and then charged to 2.5V with a constant current rate of 0.03C at a negative pressure of -0.090MPa, and then charged to 3.2V at a rate of 0.1C. Then charge it to 3.6V with a constant current at a rate of 0.2C, and seal the battery when the voltage reaches 3.6V.
第二步，对封口后的电池在10℃下进行48h的老化处理，然后先以1C的倍率恒流充电至3.8V，再以0.5C的倍率恒流充电至4.2V，最后在4.2V下恒压充电，充电截止电流为200mA。In the second step, the sealed battery is aged at 10°C for 48 hours, then charged to 3.8V at a rate of 1C, and then charged to 4.2V at a rate of 0.5C, and finally charged at 4.2V Constant voltage charging, charging cut-off current is 200mA.
实施例4，本实施例提供的一种锂离子二次电池的首次充电化成方法，包括以下步骤：第一步，将已注有电解液的锂离子二次电池在温度为70℃和相对湿度小于或等于10%的环境下陈化处理96h，然后在-0.099MPa的负压状态下，先以0.03C的倍率恒流充电至2.5V，再以0.1C的倍率恒流充电至3.2V，然后以0.2C的倍率恒流充电至3.6V，当电压到达3.6V时，对电池进行封口。Embodiment 4, a method for forming a lithium-ion secondary battery for the first time provided in this embodiment includes the following steps: the first step, the lithium-ion secondary battery that has been injected with electrolyte is heated at a temperature of 70°C and a relative humidity Aged for 96 hours in an environment less than or equal to 10%, and then charged to 2.5V with a constant current rate of 0.03C at a negative pressure of -0.099MPa, and then charged to 3.2V at a rate of 0.1C. Then charge it to 3.6V with a constant current at a rate of 0.2C, and seal the battery when the voltage reaches 3.6V.
第二步，对封口后的电池在30℃下进行480h的老化处理，然后先以1C的倍率恒流充电至3.8V，再以0.5C的倍率恒流充电至4.2V，最后在4.2V下恒压充电，充电截止电流为150mA。In the second step, the sealed battery is aged at 30°C for 480 hours, then charged to 3.8V at a rate of 1C, and then charged to 4.2V at a rate of 0.5C, and finally charged at 4.2V Constant voltage charging, charging cut-off current is 150mA.
实施例5，本实施例提供的一种锂离子二次电池的首次充电化成方法，包括以下步骤：第一步，将已注有电解液的锂离子二次电池在温度为30℃和相对湿度小于或等于7%的环境下陈化处理2h，然后在-0.01MPa的负压状态下，先以0.01C的倍率恒流充电至2.5V，再以0.05C的倍率恒流充电至3.2V，然后以0.1C的倍率恒流充电至3.6V，当电压到达3.6V时，对电池进行封口。Embodiment 5, a method for forming a lithium-ion secondary battery for the first time provided in this embodiment includes the following steps: the first step is to place the lithium-ion secondary battery filled with electrolyte at a temperature of 30°C and a relative humidity Aged for 2 hours in an environment less than or equal to 7%, and then charged at a rate of 0.01C to 2.5V at a constant current rate of 0.01C, and then charged to 3.2V at a rate of 0.05C under a negative pressure of -0.01MPa. Then charge to 3.6V with a constant current at a rate of 0.1C, and seal the battery when the voltage reaches 3.6V.
第二步，对封口后的电池在20℃下进行2h的老化处理，然后先以0.5C的倍率恒流充电至4.0V，再以0.2C的倍率恒流充电至4.2V，最后在4.2V下恒压充电，充电截止电流为50mA。In the second step, the sealed battery is aged at 20°C for 2 hours, then charged to 4.0V at a rate of 0.5C, and then charged to 4.2V at a rate of 0.2C, and finally charged at 4.2V Under constant voltage charging, the charging cut-off current is 50mA.
实施例6，本实施例提供的一种锂离子二次电池的首次充电化成方法，包括以下步骤：第一步，将已注有电解液的锂离子二次电池在温度为55℃和相对湿度小于或等于5%的环境下陈化处理48h，然后在-0.05MPa的负压状态下，先以0.02C的倍率恒流充电至2.5V，再以0.07C的倍率恒流充电至3.2V，然后以0.13C的倍率恒流充电至3.6V，当电压到达3.6V时，对电池进行封口。Embodiment 6, a method for forming a lithium-ion secondary battery for the first time provided in this embodiment includes the following steps: the first step is to place the lithium-ion secondary battery filled with electrolyte at a temperature of 55°C and a relative humidity Aged for 48 hours in an environment less than or equal to 5%, and then charged at a rate of 0.02C to 2.5V at a constant current rate of 0.02C, and then charged to 3.2V at a rate of 0.07C under a negative pressure of -0.05MPa. Then charge it to 3.6V with a constant current at a rate of 0.13C, and seal the battery when the voltage reaches 3.6V.
第二步，对封口后的电池在60℃下进行128h的老化处理，然后先以0.5C的倍率恒流充电至4.0V，再以0.2C的倍率恒流充电至4.2V，最后在4.2V下恒压充电，充电截止电流为30mA。In the second step, the sealed battery is subjected to aging treatment at 60°C for 128 hours, and then charged to 4.0V at a constant current rate of 0.5C, then charged to 4.2V at a rate of 0.2C, and finally charged at 4.2V Under constant voltage charging, the charging cut-off current is 30mA.
实施例7，本实施例提供的一种锂离子二次电池的首次充电化成方法，包括以下步骤：第一步，将已注有电解液的锂离子二次电池在温度为40℃和相对湿度小于或等于8%的环境下陈化处理8h，然后在-0.07MPa的负压状态下，先以0.02C的倍率恒流充电至2.5V，再以0.07C的倍率恒流充电至3.2V，然后以0.13C的倍率恒流充电至3.6V，当电压到达3.6V时，对电池进行封口。Embodiment 7, a method for forming a lithium-ion secondary battery for the first time provided in this embodiment includes the following steps: the first step is to place the lithium-ion secondary battery filled with electrolyte at a temperature of 40°C and relative humidity Aged for 8 hours in an environment less than or equal to 8%, and then charged at a rate of 0.02C to 2.5V at a constant current rate of 0.02C, and then charged to 3.2V at a rate of 0.07C under a negative pressure of -0.07MPa. Then charge it to 3.6V with a constant current at a rate of 0.13C, and seal the battery when the voltage reaches 3.6V.
第二步，对封口后的电池在60℃下进行10h的老化处理，然后先以0.5C的倍率恒流充电至4.0V，再以0.2C的倍率恒流充电至4.2V，最后在4.2V下恒压充电，充电截止电流为180mA。In the second step, the sealed battery is aged at 60°C for 10 hours, then charged to 4.0V at a rate of 0.5C, and then charged to 4.2V at a rate of 0.2C, and finally charged at 4.2V Under constant voltage charging, the charging cut-off current is 180mA.
对比例1，本对比例提供的一种锂离子二次电池的首次充电化成方法为：先以0.1C的倍率恒流对电池进行充电至3.8V，然后对电池进行抽真空封口，封口后再老化48h，最后以1.5C的倍率恒流充电至4.2V。Comparative example 1, the method for forming a lithium-ion secondary battery for the first time provided in this comparative example is: first charge the battery to 3.8V with a rate of 0.1C and constant current, then vacuum seal the battery, and then seal the battery. Aged for 48 hours, and finally charged to 4.2V at a constant current rate of 1.5C.
对比例2，本对比例提供的一种锂离子二次电池的首次充电化成方法为：先以0.1C的倍率恒流对电池进行充电至3.7V，然后对电池进行抽真空封口，封口后再老化48h，最后以0.2C的倍率恒流充电至4.2V。Comparative example 2, the method for the first charging and formation of a lithium-ion secondary battery provided in this comparative example is: first charge the battery to 3.7V with a rate of 0.1C and a constant current, then vacuumize and seal the battery, and then seal the battery Aged for 48 hours, and finally charged to 4.2V at a constant current rate of 0.2C.
对采用实施例1至7及对比例1和2的方法充电化成后的锂离子二次电池（分别编号为S1-S7和D1，D2）进行如下测试：（1）循环性能测试：在45℃下，以0.7C的充电倍率和1C的放电倍率对电池进行300次充放电循环，然后计算其容量保持率C1，所得结果见表1。The lithium-ion secondary batteries (respectively numbered S1-S7 and D1, D2) charged and formed by the methods of Examples 1 to 7 and Comparative Examples 1 and 2 were tested as follows: (1) Cycle performance test: at 45°C The battery was charged and discharged 300 times at a charge rate of 0.7C and a discharge rate of 1C, and then its capacity retention rate C1 was calculated. The results are shown in Table 1.
（2）内阻测试：采用电池内阻测试仪对编号为S1-S7和D1，D2的锂离子二次电池进行直流内阻测试，所得结果见表1。(2) Internal resistance test: The lithium-ion secondary batteries numbered S1-S7, D1, and D2 were tested for DC internal resistance with a battery internal resistance tester, and the results are shown in Table 1.
（3）大倍率放电性能测试：将编号为S1-S7和D1，D2分别以2C的充电倍率恒流充电至4.2V，再以0.5C恒压充电，然后以1C的放电倍率放电至3.0V，反复100次这样的充放电循环，测定第一次循环时的放电容量和第100次循环时的放电容量，求出循环后的容量保持率C2，所得结果见表1。(3) Large-rate discharge performance test: Charge numbers S1-S7, D1, and D2 to 4.2V at a charge rate of 2C, charge at a constant voltage of 0.5C, and discharge to 3.0V at a rate of 1C. , Repeated 100 such charge-discharge cycles, measured the discharge capacity at the first cycle and the discharge capacity at the 100th cycle, and calculated the capacity retention rate C2 after the cycle. The results are shown in Table 1.
（4）极片析锂测试：拆解经过循环性能测试的各电池，观察各电池的负极片上是否发生了析锂，所得结果见表1。(4) Lithium separation test on the electrode sheet: Disassemble each battery that has passed the cycle performance test, and observe whether lithium separation occurs on the negative electrode sheet of each battery. The results are shown in Table 1.
由表1可以看出，采用本发明的方法对锂离子二次电池进行充电化成后，不仅能够有效地改善锂离子二次电池的循环性能，降低其内阻，而且还能改善电池的大倍率放电性能。此外，采用本发明的方法还能防止负极片上析锂现象的发生，从而提高电池的安全性能，而且与老化后采用小电流充电的对比例2相比，本发明还能缩短电池的生产周期。As can be seen from Table 1, after the lithium-ion secondary battery is charged and formed by the method of the present invention, it can not only effectively improve the cycle performance of the lithium-ion secondary battery, reduce its internal resistance, but also improve the large rate of the battery. discharge performance. In addition, adopting the method of the present invention can also prevent the occurrence of lithium precipitation on the negative electrode sheet, thereby improving the safety performance of the battery, and compared with Comparative Example 2, which is charged with a small current after aging, the present invention can also shorten the production cycle of the battery.
这是因为本发明采用分段充电化成的方法先将电池充电至3.6V，可以将在形成固体电解质界面膜（SEI膜）的过程中产生的有害气体及时排出，更好的保证Li+的迁移，使形成的SEI膜更加均一、稳定和致密，从而有效地避免有害气体对电池的尺寸、内阻和倍率及充放电反应造成的不良影响，提高其循环性能和大倍率放电性能。而且，本发明在电池老化后，先以大电流充电、再以小电流充电，充分结合了大电流充电和小电流充电的优点，避开了二者的缺点，不仅可以缩短电池的生产周期，也可以避免负极析锂问题的发生，从而保证电池的循环寿命和安全性能等各种性能。This is because the present invention first charges the battery to 3.6V by adopting the staged charge formation method, which can discharge the harmful gas generated in the process of forming the solid electrolyte interfacial film (SEI film) in time, and better ensure the migration of Li+ , so that the formed SEI film is more uniform, stable and dense, thereby effectively avoiding the adverse effects of harmful gases on the size, internal resistance, rate and charge-discharge reaction of the battery, and improving its cycle performance and high-rate discharge performance. Moreover, after the battery is aging, the present invention first charges with a large current and then charges with a small current, which fully combines the advantages of large current charging and low current charging, avoids the shortcomings of both, and can not only shorten the production cycle of the battery, It can also avoid the occurrence of the problem of lithium precipitation at the negative electrode, thereby ensuring various performances such as the cycle life and safety performance of the battery.
表1：编号为S1-S7和D1，D2的电池的循环性能测试、内阻测试、大倍率放电性能测试以及极片析锂情况测试的结果。Table 1: The results of the cycle performance test, internal resistance test, high rate discharge performance test and lithium separation test of the batteries numbered S1-S7 and D1, D2.
需要说明的是，根据上述说明书的揭示和教导，本发明所属领域的技术人员还可以对上述实施方式进行变更和修改。因此，本发明并不局限于上面揭示和描述的具体实施方式，对本发明的一些等同修改和变更也应当落入本发明的权利要求的保护范围内。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本发明构成任何限制。It should be noted that, according to the disclosure and teaching of the above specification, those skilled in the art to which the present invention pertains may also make changes and modifications to the above implementation manners. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some equivalent modifications and changes to the present invention should also fall within the protection scope of the claims of the present invention. In addition, although some specific terms are used in this specification, these terms are only for convenience of description and do not constitute any limitation to the present invention.
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