技术领域technical field
本发明属于电池充电技术领域，具体涉及一种石墨负极体系锂离子电池的充电方法。The invention belongs to the technical field of battery charging, and in particular relates to a charging method for a graphite negative electrode system lithium ion battery.
背景技术Background technique
现有技术中，存在三种锂离子电池充电方法，分别为基于抑制温升的充电方法、基于SOC(电池荷电状态或剩余电量)的充电方法和基于抑制极化电压的充电方法。In the prior art, there are three charging methods for lithium-ion batteries, namely, a charging method based on suppressing temperature rise, a charging method based on SOC (battery state of charge or remaining power), and a charging method based on suppressing polarization voltage.
其中，基于抑制温升的充电方法实时估算锂离子电池充电各个阶段的温升，将温升最小充电时间最短作为目标来设计充电各个阶段的电流。基于SOC的充电方法认为SOC越低锂离子电池所能承受的最大充电电流越大，即从SOC＝0％到SOC＝100％的整个充电过程中，该充电方法的充电电流随SOC的增大而逐渐减小。基于抑制极化电压的充电方法认为极化电压是限制锂离子电池大电流充电的主要原因，该方法以降低充电时的极化电压为目的，将传统恒流恒压充电中的恒流阶段分成多段恒流充电，各恒流充电阶段中间加入电流为零的停充阶段或者电流为负的短暂放电阶段。Among them, the charging method based on suppressing temperature rise estimates the temperature rise of each stage of lithium-ion battery charging in real time, and designs the current of each stage of charging with the minimum temperature rise and the shortest charging time as the goal. The charging method based on SOC believes that the lower the SOC, the greater the maximum charging current that the lithium-ion battery can withstand, that is, during the entire charging process from SOC=0% to SOC=100%, the charging current of this charging method increases with the SOC And gradually decrease. The charging method based on suppressing the polarization voltage believes that the polarization voltage is the main reason for limiting the high current charging of lithium-ion batteries. This method aims to reduce the polarization voltage during charging, and divides the constant current stage in the traditional constant current and constant voltage charging into two stages: Multi-stage constant current charging, each constant current charging stage is added with a stop charging stage with zero current or a short discharge stage with negative current.
上述锂离子电池的充电方法大部分在制定过程中只考虑了充电过程中的温升、SOC、极化电压等电池的外部参数，很少考虑到锂离子电池内部的电化学特性，尤其针对石墨负极体系锂离子电池，若采用上述方法给电池充电，无法避免石墨负极晶体结构的破坏和析锂造成的电池容量损失，导致电池寿命降低。Most of the charging methods of the above-mentioned lithium-ion batteries only consider the external parameters of the battery such as temperature rise, SOC, and polarization voltage during the charging process, and seldom take into account the electrochemical characteristics of the lithium-ion battery, especially for graphite If the lithium-ion battery of the negative electrode system is charged by the above method, the destruction of the crystal structure of the graphite negative electrode and the loss of battery capacity caused by lithium precipitation cannot be avoided, resulting in a reduction in battery life.
发明内容Contents of the invention
对于基于抑制温升的充电方法，温度过高(60℃以上)时接近满电状态的锂离子电池正极材料氧化性大大增强，的确有可能氧化电解液放出气体和热量，导致电解液变质电池鼓包甚至热失控。但是在55℃以下，电池的温升反而是有利于锂离子从正极脱嵌、在电解液中扩散和嵌入负极材料内部，即有利于充电过程的进行。这也是为何电池内阻随温度的升高而降低。所以温升不应作为制定充电方法的依据，正确的做法的设定一个较高的温度上限作为安全阈值，仅当电池温度超过该安全阈值时才考虑温度对充电过程的影响。For the charging method based on suppressing temperature rise, when the temperature is too high (above 60°C), the oxidation of the positive electrode material of the lithium-ion battery close to the fully charged state is greatly enhanced, and it is indeed possible to oxidize the electrolyte to release gas and heat, causing the electrolyte to deteriorate and the battery to bulge Even thermal runaway. However, below 55°C, the temperature rise of the battery is conducive to the deintercalation of lithium ions from the positive electrode, diffusion in the electrolyte, and insertion into the negative electrode material, which is beneficial to the charging process. This is why the internal resistance of the battery decreases as the temperature increases. Therefore, the temperature rise should not be used as the basis for formulating the charging method. The correct way is to set a higher temperature upper limit as the safety threshold. Only when the battery temperature exceeds the safety threshold, the influence of temperature on the charging process is considered.
对于基于SOC的充电方法，随着充电的进行，当锂离子电池SOC超过一定值(20％左右)时，由于随着充电过程的进行负极石墨颗粒中容易嵌锂的位置逐渐减少，锂离子电池可承受的最大充电电流也的确逐渐减小。但是，当锂离子电池电量比较低(SOC约在20％以内)时，石墨负极体系的锂离子电池所能承受的最大充电电流是随SOC的增大而增大的。这需要从石墨负极锂离子电池的电化学特性方面进行解释。负极石墨颗粒是层状结构，当SOC＝0时，石墨颗粒层状结构中含锂量很少，石墨层间距处于最小值。从SOC＝0到SOC等于某一值(约20％)的充电过程中，随着SOC逐渐增大，石墨层中嵌锂量逐渐增多，石墨层间距也逐渐变大；而且随着SOC增大，石墨层间距变大的速度逐渐减小。当SOC超过某一值(约20％)时，石墨层间含锂量足够，石墨层间距基本不再随SOC而变大，处于最大值。因此在很低的SOC下若直接开始大电流快速充电，石墨颗粒表面的石墨层快速嵌锂而导致层间距迅速变大；而石墨颗粒内部的石墨层来不及嵌入足够的锂，石墨层间距仍然很小。这样，石墨颗粒表层和内部之间的应力很大，有可能引起C-C化学键断裂、石墨晶体结构破坏，从而导致可用石墨负极材料的损失。低SOC大电流快速充电导致的石墨晶体结构的破坏可以从石墨负极材料的拉曼光谱中观测得到。For the SOC-based charging method, as the charging progresses, when the SOC of the lithium-ion battery exceeds a certain value (about 20%), due to the gradual reduction of the position where lithium is easily inserted in the negative electrode graphite particles as the charging process progresses, the lithium-ion battery The maximum charging current that can be tolerated is indeed gradually reduced. However, when the lithium-ion battery has a relatively low charge (SOC within about 20%), the maximum charging current that the lithium-ion battery of the graphite negative electrode system can withstand increases with the increase of the SOC. This needs to be explained from the electrochemical characteristics of lithium-ion batteries with graphite anodes. Negative electrode graphite particles have a layered structure. When SOC=0, the lithium content in the layered structure of graphite particles is very small, and the distance between graphite layers is at a minimum. During the charging process from SOC=0 to SOC equal to a certain value (about 20%), as the SOC gradually increases, the amount of lithium intercalated in the graphite layer gradually increases, and the distance between the graphite layers gradually increases; and as the SOC increases , the speed at which the interlayer spacing of graphite becomes larger gradually decreases. When the SOC exceeds a certain value (about 20%), the lithium content between the graphite layers is sufficient, and the interlayer spacing of the graphite basically no longer increases with the SOC, and is at the maximum value. Therefore, if a high-current fast charge is started directly at a very low SOC, the graphite layer on the surface of the graphite particle will intercalate lithium quickly, resulting in a rapid increase in interlayer spacing; while the graphite layer inside the graphite particle has no time to intercalate enough lithium, the graphite interlayer spacing is still very large. Small. In this way, the stress between the surface layer and the interior of graphite particles is very large, which may cause the C-C chemical bond to break and the graphite crystal structure to be destroyed, resulting in the loss of available graphite anode materials. The destruction of graphite crystal structure caused by fast charging with low SOC and high current can be observed from the Raman spectrum of graphite anode materials.
另外，当SOC低于10％时，随着SOC的减小，负极石墨颗粒表面电荷转移阻抗迅速增大；相同的充电电流下，负极的电势也必将随电荷转移阻抗的增大而迅速降低，当负极电势低于0伏(相对于Li/Li+)时，负极材料表面将有发生析锂的风险。所以，随着SOC的降低，充电电流也应当降低，以抵消负极电势降低的趋势，防止负极析锂。为了防止石墨晶体结构遭到破坏和低SOC下发生析锂，石墨负极锂离子电池在低SOC阶段所能承受的最大充电电流，应当是随着SOC的增大逐渐增大的类似于指数关系的一段曲线。In addition, when the SOC is lower than 10%, as the SOC decreases, the charge transfer resistance on the surface of the negative electrode graphite particles increases rapidly; under the same charging current, the potential of the negative electrode will also decrease rapidly with the increase of the charge transfer resistance. , when the potential of the negative electrode is lower than 0 volts (relative to Li/Li+ ), there will be a risk of lithium precipitation on the surface of the negative electrode material. Therefore, with the reduction of SOC, the charging current should also be reduced to offset the trend of negative electrode potential reduction and prevent the negative electrode from decomposing lithium. In order to prevent the graphite crystal structure from being destroyed and lithium precipitation under low SOC, the maximum charging current that graphite negative lithium-ion batteries can withstand at the low SOC stage should be similar to an exponential relationship that gradually increases with the increase of SOC. a curve.
对于基于抑制极化电压的充电方法，采用充-停-充或者充-放-充的充电方法的确能够抑制负极石墨颗粒中的锂浓度极化；通过暂停嵌锂或将石墨颗粒表层的高浓度锂脱嵌掉一部分从而减小石墨颗粒表层中锂的浓度，使锂浓度趋向于均匀，防止石墨颗粒表层过充电而出现析锂或生成锂支晶。但这种对锂浓度极化的抑制仅在停充或放电时段及该时段的附近起作用，在其他恒流充电阶段，负极石墨颗粒中必将迅速重新建立锂浓度极化。这样在充-停-充-停(或充-放-充-放)的充电循环中，若充电时间/停充时间(或充电时间/放电时间)设置过大，起不到防止析锂的作用；若设置的过小，充电时间和放电发热都将大大增大。为了缩短充电时间，充-停-充-停(或充-放-充-放)的充电方法中往往将充电阶段的电流设置的更大，这样石墨颗粒中重新建立的锂浓度极化也将更大，更有可能导致析锂。另外这种正负脉冲的充电方法将使充电设备变的非常复杂。For the charging method based on suppressing the polarization voltage, the charging method of charge-stop-charge or charge-discharge-charge can indeed suppress the lithium concentration polarization in the graphite particles of the negative electrode; A part of lithium is deintercalated to reduce the concentration of lithium in the surface layer of graphite particles, so that the concentration of lithium tends to be uniform, and prevent the surface layer of graphite particles from being overcharged to cause lithium precipitation or lithium branch crystals. However, this suppression of lithium concentration polarization only works during the charging stop or discharge period and its vicinity. In other constant current charging stages, the lithium concentration polarization will be quickly re-established in the graphite particles of the negative electrode. In this way, in the charging cycle of charge-stop-charge-stop (or charge-discharge-charge-discharge), if the charging time/stop charging time (or charging time/discharging time) is set too large, it will not be able to prevent lithium precipitation. Function; if the setting is too small, the charging time and discharge heat will be greatly increased. In order to shorten the charging time, the charging method of charge-stop-charge-stop (or charge-discharge-charge-discharge) often sets the current in the charging stage to be larger, so that the lithium concentration polarization re-established in the graphite particles will also be reduced. Larger, more likely to lead to lithium precipitation. In addition, this positive and negative pulse charging method will make the charging equipment very complicated.
实际上，充电时适当的极化不仅不会导致负极析理，反而有利于提高锂离子电池的充电速度；石墨颗粒内外部的极化锂浓度差有利于提高锂向石墨颗粒内部的扩散速度。其实，只要以锂离子电池所能承受的最大充电电流持续充电就能在保证不析锂不伤害电池的前提下以最短的时间完成充电；这期间产生的极化是有利于加快充电速度的。In fact, proper polarization during charging will not cause negative electrode disintegration, but will help to increase the charging speed of lithium-ion batteries; the difference in polarized lithium concentration inside and outside graphite particles will help increase the diffusion rate of lithium into graphite particles. In fact, as long as the lithium-ion battery can be continuously charged with the maximum charging current that the lithium-ion battery can withstand, the charging can be completed in the shortest time under the premise of ensuring that the lithium-ion battery does not decompose and does not damage the battery; the polarization generated during this period is conducive to accelerating the charging speed.
基于上述考虑，本发明的目的是提供一种石墨负极体系锂离子电池的充电方法，用于解决现有石墨负极体系锂离子电池充电方法容易导致负极析理和破坏石墨负极晶体结构导致电池寿命降低的问题。Based on the above considerations, the object of the present invention is to provide a charging method for graphite negative electrode system lithium ion battery, which is used to solve the problem that the existing graphite negative electrode system lithium ion battery charging method is easy to cause negative electrode analysis and destroy the graphite negative electrode crystal structure, resulting in reduced battery life. The problem.
为解决上述技术问题，本发明提出一种石墨负极体系锂离子电池的充电方法，包括以下步骤：In order to solve the problems of the technologies described above, the present invention proposes a charging method for a graphite negative electrode system lithium-ion battery, comprising the following steps:
进行恒流充电，恒流充电的过程包括初始充电阶段和中间充电阶段，检测电池剩余电量，当电池剩余电量小于或等于第一设定值时为初始充电阶段，当电池剩余电量大于第一设定值时为中间充电阶段；Carry out constant current charging. The process of constant current charging includes the initial charging stage and the intermediate charging stage. The remaining battery power is detected. When the remaining battery power is less than or equal to the first setting value, it is the initial charging stage. When the remaining battery power is greater than the first setting When the value is fixed, it is the intermediate charging stage;
将初始充电阶段划分成两个小阶段以上的第一组恒流充电阶段，即第一组恒流充电阶段中包含两个以上的子阶段(小阶段)，第一组恒流充电阶段中每个子阶段对应设置的充电倍率随着电池剩余电量增大而增大；Divide the initial charging stage into the first group of constant current charging stages with more than two small stages, that is, the first group of constant current charging stages contains more than two substages (small stages), and each of the first group of constant current charging stages The charging rate corresponding to each sub-stage will increase as the remaining battery power increases;
将中间充电阶段划分成两个小阶段以上的第二组恒流充电阶段，即第二组恒流充电阶段中包含两个以上的子阶段(小阶段)，第二组恒流充电阶段中每个子阶段对应设置的充电倍率随着电池剩余电量增大而减小。The intermediate charging stage is divided into the second group of constant current charging stages with more than two small stages, that is, the second group of constant current charging stages contains more than two substages (small stages), and each of the second group of constant current charging stages The charging rate corresponding to each sub-stage will decrease as the remaining battery power increases.
本发明基于石墨负极体系锂离子电池内部的电化学特性的考虑，通过设置第一组恒流充电阶段和第二组恒流充电阶段，在第一组恒流充电阶段中，对应设置的充电倍率随着电池剩余电量增大而增大，在第二组恒流充电阶段中对应设置的充电倍率随着电池剩余电量增大而减小，避免了石墨负极晶体结构的破坏和析锂造成的电池容量损失，既能够提高石墨负极体系锂离子电池的循环寿命，又能够缩短中间充电阶段内的充电时间。The present invention is based on the consideration of the electrochemical characteristics inside the lithium-ion battery of the graphite negative electrode system. By setting the first set of constant current charging stages and the second set of constant current charging stages, in the first set of constant current charging stages, the corresponding set charging rate As the remaining power of the battery increases, the charging rate correspondingly set in the second set of constant current charging stages decreases as the remaining power of the battery increases, avoiding the destruction of the crystal structure of the graphite negative electrode and the damage to the battery caused by lithium precipitation. The capacity loss can not only improve the cycle life of the graphite negative electrode system lithium-ion battery, but also shorten the charging time in the intermediate charging stage.
进一步，恒流充电过程中，检测电池的端电压，当电池的端电压达到设定的充电截止电压时，停止恒流充电，进行恒压充电。Further, during the constant current charging process, the terminal voltage of the battery is detected, and when the terminal voltage of the battery reaches the set charging cut-off voltage, the constant current charging is stopped and the constant voltage charging is performed.
进一步，所述第一设定值的电池剩余电量范围为15％～25％。Further, the range of the remaining battery capacity of the first set value is 15%-25%.
作为对第一组恒流充电阶段对应设置的充电倍率的进一步限定，第一组恒流充电阶段对应设置的充电倍率与电池剩余电量为递增的第一指数函数关系。As a further limitation on the charging rate corresponding to the first group of constant current charging stages, the relationship between the charging rate corresponding to the first group of constant current charging stages and the remaining power of the battery is an increasing first exponential function.
作为对第二组恒流充电阶段对应设置的充电倍率的进一步限定，第二组恒流充电阶段对应设置的充电倍率与电池剩余电量为递减的第二指数函数关系。As a further limitation on the charging rate corresponding to the second group of constant current charging stages, the relationship between the charging rate corresponding to the second group of constant current charging stages and the remaining power of the battery is a second exponential function relationship that decreases.
为了保证电池在低SOC充电时的充电倍率足够小，进一步，所述第一指数函数关系的曲率大于第二指数函数关系的曲率。In order to ensure that the charging rate of the battery is sufficiently small when charging at a low SOC, further, the curvature of the first exponential function relationship is greater than the curvature of the second exponential function relationship.
为了防止电池温度过高对电池寿命产生的影响，进一步，所述恒流充电的过程中，当电池温度达到设定的第一温度上限时，降低当前设置的充电倍率继续充电；当电池温度达到设定的第二温度上限时，停止充电；设定的第二温度上限大于第一温度上限。In order to prevent the impact of excessive battery temperature on battery life, further, during the constant current charging process, when the battery temperature reaches the set first temperature upper limit, reduce the currently set charging rate and continue charging; when the battery temperature reaches When the set second temperature upper limit is reached, the charging is stopped; the set second temperature upper limit is greater than the first temperature upper limit.
具体的，当电池温度大于等于第一温度上限且小于第二温度上限时，根据检测的环境温度确定充电倍率的降低幅度，且环境温度越高充电倍率的降幅越大。Specifically, when the battery temperature is greater than or equal to the first temperature upper limit and less than the second temperature upper limit, the reduction range of the charging rate is determined according to the detected ambient temperature, and the higher the ambient temperature, the greater the reduction rate of the charging rate.
为了防止电池低温充电时发生析锂，进一步，当电池温度小于设定的温度下限时，降低当前设置的充电倍率继续充电。且当电池温度小于设定的温度下限时，根据电池温度与温度下限的差值确定充电倍率的降低幅度，且差值越大充电倍率的降幅越大。In order to prevent lithium deposition when the battery is charged at low temperature, further, when the battery temperature is lower than the set temperature lower limit, the currently set charging rate is reduced to continue charging. And when the battery temperature is lower than the set temperature lower limit, the decrease rate of the charging rate is determined according to the difference between the battery temperature and the temperature lower limit, and the greater the difference is, the greater the decrease rate of the charge rate is.
附图说明Description of drawings
图1是本发明的实验一提供的一种充电方法示意图；Fig. 1 is a schematic diagram of a charging method provided in Experiment 1 of the present invention;
图2是实验二提供的常规充电方法示意图；Figure 2 is a schematic diagram of a conventional charging method provided in Experiment 2;
图3是采用实验一和实验二的充电方法进行循环充放电所得到的放电容量保持率测试结果图。Fig. 3 is a test result graph of the discharge capacity retention rate obtained by carrying out cyclic charge and discharge using the charging methods of Experiment 1 and Experiment 2.
具体实施方式Detailed ways
下面结合附图对本发明的具体实施方式作进一步的说明。The specific embodiments of the present invention will be further described below in conjunction with the accompanying drawings.
本发明提出一种石墨负极体系锂离子电池的充电方法，包括以下步骤：The present invention proposes a charging method for a graphite negative electrode system lithium ion battery, comprising the following steps:
将石墨负极锂离子电池的充电过程分成三个充电阶段，分别为初始充电阶段、中间充电阶段和最后充电阶段，初始充电阶段包含若干个充电倍率逐渐增大的恒流充电小阶段，中间充电阶段包含若干个充电倍率逐渐减小的恒流充电小阶段，最后充电阶段为恒压充电阶段。The charging process of the lithium-ion battery with graphite negative electrode is divided into three charging stages, which are the initial charging stage, the intermediate charging stage and the final charging stage. It includes several small stages of constant current charging with gradually decreasing charging rate, and the final charging stage is the constant voltage charging stage.
初始充电阶段与中间充电阶段的转变依据是SOC＝15％～25％，中间充电阶段与最后充电阶段的转变依据是电池的端电压达到设定的充电截止电压。The basis for the transition between the initial charging stage and the intermediate charging stage is SOC=15%-25%, and the basis for the transition between the intermediate charging stage and the final charging stage is that the terminal voltage of the battery reaches the set charging cut-off voltage.
为了避免低SOC充电时析锂和石墨晶体结构遭到破坏，初始充电过程中各恒流充电阶段的最大充电倍率相对于SOC逐步增大的趋势应接近递增的指数函数关系f1(x)。为了避免较大SOC充电时因为石墨颗粒局部过充电而出现的析锂，中间充电过程中各恒流充电阶段的最大充电倍率相对于SOC逐步减小的趋势应接近递减的指数函数关系f2(x)，其中，f1(x)函数曲线的曲率要大于f2(x)，这是因为充电对石墨晶体结构的破坏主要发生在较低的SOC阶段，f1(x)函数曲线的曲率较大能够保证低SOC充电时的充电倍率足够小。实际应用中先确定函数方程f1(x)、f2(x)和初始充电过程、中间充电过程中的SOC的划分间隔，再根据函数方程和SOC的划分间隔确定初始充电过程、中间充电过程中各恒流充电阶段的充电倍率。In order to avoid the destruction of lithium and graphite crystal structures during low SOC charging, the trend of the maximum charging rate in each constant current charging stage during the initial charging process relative to the gradual increase in SOC should be close to the increasing exponential function relationship f1 (x). In order to avoid the occurrence of lithium precipitation due to local overcharging of graphite particles when charging with a large SOC, the trend of the maximum charging rate in each constant current charging stage in the intermediate charging process relative to the gradual decrease of the SOC should be close to a decreasing exponential function relationship f2 ( x), wherein the curvature of the f1 (x) function curve is greater than f2 (x), this is because the damage to the graphite crystal structure by charging mainly occurs at a lower SOC stage, and the curvature of the f1 (x) function curve Larger can ensure that the charging rate is small enough when charging with low SOC. In practical application, first determine the functional equations f1 (x), f2 (x) and the division interval of the SOC in the initial charging process and the intermediate charging process, and then determine the initial charging process and the intermediate charging process according to the functional equation and the division interval of the SOC The charging rate of each constant current charging stage.
设定第一温度上限Tmax1和第二温度上限Tmax2，充电过程中监控电池温度，当电池温度达到温度上限Tmax1时降低充电倍率继续充电，环境温度越高或电池散热条件越差，降幅越大；当电池温度达到温度上限Tmax2时停止充电。Set the first temperature upper limit Tmax1 and the second temperature upper limit Tmax2 , monitor the battery temperature during the charging process, reduce the charging rate and continue charging when the battery temperature reaches the upper temperature limit Tmax1 , the higher the ambient temperature or the worse the battery cooling condition, the lower the rate The larger; stop charging when the battery temperature reaches the upper limit Tmax2 .
设定一个温度下限Tmin，充电过程中监控电池温度，当电池温度小于Tmin时应降低充电倍率，且电池温度与Tmin的差值越大降幅越大。Set a temperature lower limit Tmin , monitor the battery temperature during the charging process, and reduce the charging rate when the battery temperature is lower than Tmin , and the greater the difference between the battery temperature and Tmin , the greater the decrease.
为了证明本发明充电方法的有效性，进行实验一和实验二进行对比分析，实验一为本发明的充电方法，实验二为常规恒流恒压充电的充电方法，且实验一和实验二采用相同石墨负极体系的磷酸铁锂锂离子电池，电池的正极由95.3％LiFePO4+2％PVDF+2.7％SP(导电剂)混合而成，电池的负极由98％人造石墨+1％SBR+1％CMC混合而成，隔膜为PP/PE/PP复合膜，电解液由有机溶剂(30％EC+30％PC+40％DEC)、1mol/L LiPF6和添加剂(0.5％VC、5％FEC、4％VEC)组成。In order to prove the effectiveness of the charging method of the present invention, experiment one and experiment two are carried out comparative analysis, experiment one is the charging method of the present invention, experiment two is the charging method of conventional constant current and constant voltage charging, and experiment one and experiment two adopt the same Lithium iron phosphate lithium ion battery with graphite negative electrode system, the positive electrode of the battery is made of 95.3% LiFePO4 +2% PVDF+2.7% SP (conductive agent), the negative electrode of the battery is made of 98% artificial graphite + 1% SBR + 1% CMC is mixed, the diaphragm is PP/PE/PP composite film, the electrolyte is composed of organic solvent (30%EC+30%PC+40%DEC), 1mol/L LiPF6 and additives (0.5%VC, 5%FEC, 4% VEC) composition.
具体的，实验一的过程如下：Specifically, the process of Experiment 1 is as follows:
在室温23℃下，按照本发明锂离子电池充电方法对电池充电，充电过程如图1所示，具体包括以下步骤：At a room temperature of 23°C, the battery is charged according to the lithium-ion battery charging method of the present invention, and the charging process is shown in Figure 1, which specifically includes the following steps:
选定从初始充电阶段转变到中间充电阶段的依据是SOC＝20％，选定SOC＝20％～30％时的充电倍率为2.5C。The basis for selecting the transition from the initial charging stage to the intermediate charging stage is SOC = 20%, and the charging rate when SOC = 20% to 30% is selected is 2.5C.
在图1中的“充电倍率-SOC”坐标系中，以点(0,0.05)和(0.2,2.5)确定初始充电过程中的指数函数曲线f1(x)，该曲线可以看作是初始充电过程中电池可承受的最大充电倍率曲线。由于石墨晶体结构的破坏主要发生在很低的SOC范围内，该指数函数曲线的曲率应较大，设定该指数函数曲线方程为：In the "charging rate-SOC" coordinate system in Figure 1, the exponential function curve f1 (x) in the initial charging process is determined by points (0,0.05) and (0.2,2.5), which can be regarded as the initial The maximum charging rate curve that the battery can withstand during charging. Since the destruction of the graphite crystal structure mainly occurs in a very low SOC range, the curvature of the exponential function curve should be larger, and the equation of the exponential function curve is set as:
f1(x)＝b1+a1e5xf1 (x)=b1 +a1 e5x
解方程，由得到即f1(x)＝-1.3758+1.4258e5x。solve the equation by get That is, f1 (x)=-1.3758+1.4258e5x .
在图1中的“充电倍率-SOC”坐标系中，以点(0.3,2.5)和(1,0.05)确定中间充电过程的指数函数曲线f2(x)，该曲线可以看作是中间充电过程中电池可承受的最大充电倍率曲线。该曲线f2(x)的曲率应比f1(x)曲线的曲率小，设定该指数函数曲线方程为：In the "charging rate-SOC" coordinate system in Figure 1, the exponential function curve f2 (x) of the intermediate charging process is determined by points (0.3, 2.5) and (1, 0.05), which can be regarded as the intermediate charging The maximum charging rate curve that the battery can withstand during the process. The curvature of the curve f2 (x) should be smaller than the curvature of the f1 (x) curve, and the equation of the exponential function curve is set as:
f2(x)＝b2+a2e-xf2 (x)=b2 +a2 e-x
解方程，由得到即f2(x)＝-2.3668+6.5694e-x。solve the equation by get That is, f2 (x)=-2.3668+6.5694e-x .
选定SOC的划分间隔为10％，再根据f1(x)和f2(x)的方程即可确定初始充电过程和中间充电过程中各恒流充电阶段的充电倍率(具体数值标注在图1中)，各恒流充电阶段的充电倍率值应当在电池可承受最大充电倍率曲线以下(见图1)。由于充电对石墨晶体结构的破坏主要集中在较低的SOC阶段，本发明将0％～10％SOC分成0％～5％SOC和5％～10％SOC两个恒流充电阶段。由于0.05C的充电倍率太小，本发明将0％～5％SOC和90％～100％SOC两个恒流充电阶段的充电倍率设置为0.1C。The division interval of the selected SOC is 10%, and then according to the equations of f1 (x) and f2 (x), the charging rate of each constant current charging stage in the initial charging process and the intermediate charging process can be determined (the specific values are marked in Fig. 1), the charge rate value of each constant current charging stage should be below the maximum charge rate curve that the battery can withstand (see Figure 1). Since the damage to the graphite crystal structure by charging is mainly concentrated in the lower SOC stage, the present invention divides 0%-10% SOC into two constant-current charging stages of 0%-5% SOC and 5%-10% SOC. Since the charging rate of 0.05C is too small, the present invention sets the charging rate of the two constant current charging stages of 0% to 5% SOC and 90% to 100% SOC as 0.1C.
由于实验一采用磷酸铁锂电池，可选定充电截止电压为3.65v，充电过程中当电池端电压达到设定的充电截止电压3.65v时，转为恒压充电，当充电倍率降到0.05C时停止充电。Since Experiment 1 uses a lithium iron phosphate battery, the charging cut-off voltage can be selected as 3.65v. When the battery terminal voltage reaches the set charging cut-off voltage of 3.65v during the charging process, it will switch to constant voltage charging. When the charging rate drops to 0.05C stop charging.
本发明的实验采用的是磷酸铁锂电池，环境温度为23℃，可据此设定温度上限Tmax1＝45℃、Tmax2＝50℃。在整个充电过程中实时检测电池温度，当电池温度达到45℃时充电倍率降为图1中对应充电倍率的80％。当电池温度重新下降到45℃以下并延续10分钟后，根据当前SOC重新按照图1中的充电倍率对电池充电。The experiment of the present invention uses a lithium iron phosphate battery, and the ambient temperature is 23°C. Based on this, the upper temperature limit Tmax1 =45°C and Tmax2 =50°C can be set. During the whole charging process, the battery temperature is detected in real time. When the battery temperature reaches 45°C, the charging rate is reduced to 80% of the corresponding charging rate in Figure 1. When the battery temperature drops below 45°C for 10 minutes, recharge the battery according to the charging rate in Figure 1 according to the current SOC.
选取30支电池进行500次充放电循环试验，具体步骤为：Select 30 batteries for 500 charge-discharge cycle tests, the specific steps are:
采用本发明实验一的充电方法对电池进行充电，从0％SOC充到100％SOC，搁置20min，以1C放电倍率放电到SOC＝10％，然后改用小倍率0.2C放电到电池端电压为2.5v，再搁置20min。Adopt the charging method of Experiment 1 of the present invention to charge the battery, charge from 0% SOC to 100% SOC, put it on hold for 20 minutes, discharge to SOC=10% with a discharge rate of 1C, and then use a small rate of 0.2C to discharge to a battery terminal voltage of 2.5v, and then put it on hold for 20min.
如此重复499次后，30支电池的平均放电容量保持率如图3中的曲线1所示。After repeating this 499 times, the average discharge capacity retention rate of the 30 batteries is shown in curve 1 in FIG. 3 .
实验二的过程如下：The process of Experiment 2 is as follows:
在室温23℃环境下，采用与实验一相同的锂离子电池进行常规恒流恒压充电，如图2所示，具体步骤如下：At a room temperature of 23°C, use the same lithium-ion battery as Experiment 1 for conventional constant-current and constant-voltage charging, as shown in Figure 2. The specific steps are as follows:
从0％SOC开始，以恒定倍率1C充电，一直充到截止电压3.65v。以恒定电压3.65v充电，当充电倍率降低到0.05C时停止充电。Starting from 0% SOC, charge at a constant rate of 1C until the cut-off voltage is 3.65v. Charge with a constant voltage of 3.65v, and stop charging when the charging rate drops to 0.05C.
选取30支电池进行500次充放电循环试验，具体步骤为：Select 30 batteries for 500 charge-discharge cycle tests, the specific steps are:
采用实验二的充电方法进行充电，从0％SOC充到100％SOC，然后按照实验一中记载的循环放电的放电方法进行放电，30支电池的平均放电容量保持率如图3中的曲线2所示。Use the charging method of Experiment 2 to charge, charge from 0% SOC to 100% SOC, and then discharge according to the discharge method of cyclic discharge recorded in Experiment 1. The average discharge capacity retention rate of 30 batteries is shown in curve 2 in Figure 3. shown.
从图3石墨负极体系锂离子电池室温满充满放循环试验结果可以看出，与常规的恒流恒压充电方法相比，采用本发明中的充电方法可以明显提高石墨负极体系锂离子电池的循环寿命。As can be seen from Fig. 3 graphite negative electrode system lithium-ion battery room temperature full charge and discharge cycle test results, compared with the conventional constant current and constant voltage charging method, adopting the charging method in the present invention can obviously improve the cycle of graphite negative electrode system lithium-ion battery life.
上表为实验一和实验二的充电时间对比，从表中可以看出，若将锂离子电池从放空充到满电状态，即从0％SOC充到100％SOC，则采用实验一的充电方法充电所需要的时间将远远大于实验二；但是，若从20％SOC充到80％SOC，则采用实验一的充电方法所需要的充电时间将比实验二快5.3min；特别是，若从20％SOC充到60％SOC，则采用实验一的充电方法将比实验二快10.1min。因此，本发明的充电方法尤其适合于20％～80％SOC范围内的快速充电和20％～60％SOC范围内的快速补充充电。本发明实验一在0％～100％SOC范围外的充电时间虽然长，却避免了石墨负极晶体结构的破坏和析锂造成的电池容量损失，有效的保障了电池寿命。The above table compares the charging time of Experiment 1 and Experiment 2. It can be seen from the table that if the lithium-ion battery is charged from empty to fully charged, that is, from 0% SOC to 100% SOC, the charging time of Experiment 1 will be adopted. The charging time required by the method will be much longer than that in the second experiment; however, if it is charged from 20% SOC to 80% SOC, the charging time required by the charging method of the first experiment will be 5.3 minutes faster than that of the second experiment; especially, if From 20% SOC to 60% SOC, the charging method of Experiment 1 will be 10.1min faster than Experiment 2. Therefore, the charging method of the present invention is especially suitable for fast charging within the range of 20%-80% SOC and fast supplementary charging within the range of 20%-60% SOC. Although the charging time of Experiment 1 of the present invention is long outside the range of 0% to 100% SOC, it avoids the destruction of the crystal structure of the graphite negative electrode and the loss of battery capacity caused by lithium analysis, and effectively guarantees the battery life.
综上所述，本发明的充电方法在制定过程中从电化学层面充分考虑了负极石墨颗粒的嵌锂过程和析锂过程，在保障石墨负极体系锂离子电池循环寿命的前提下提高了其在20％～80％SOC范围内充电时的充电速度。In summary, the charging method of the present invention has fully considered the lithium intercalation process and the lithium analysis process of the negative electrode graphite particles from the electrochemical level during the formulation process, and has improved its battery life in the graphite negative electrode system under the premise of ensuring the cycle life of the lithium ion battery. The charging speed when charging in the range of 20% to 80% SOC.
以上所述仅为本发明的优选实验，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的权利要求范围之内。The above descriptions are only preferred experiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the scope of the claims of the present invention.
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