WO2017143761A1 - 二次电池充电方法 - Google Patents

二次电池充电方法 Download PDF

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Publication number
WO2017143761A1
WO2017143761A1 PCT/CN2016/098448 CN2016098448W WO2017143761A1 WO 2017143761 A1 WO2017143761 A1 WO 2017143761A1 CN 2016098448 W CN2016098448 W CN 2016098448W WO 2017143761 A1 WO2017143761 A1 WO 2017143761A1
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battery
charging
current
constant current
voltage
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PCT/CN2016/098448
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English (en)
French (fr)
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骆福平
党琦
方占召
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宁德新能源科技有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
    • H02J7/007—Regulation of charging or discharging current or voltage
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
    • H02J7/007—Regulation of charging or discharging current or voltage
    • H02J7/00712—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters
    • H02J7/007182—Regulation of charging or discharging current or voltage the cycle being controlled or terminated in response to electric parameters in response to battery voltage
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention belongs to the field of battery technology, and more particularly to a secondary battery charging method.
  • the polarization accumulation of battery charging is used as the entry point.
  • the temperature rise problem in the charging process of the secondary battery can also be optimized.
  • the secondary battery is charged by continuously charging the battery to a certain potential using a constant current, and then charging the battery at a constant voltage.
  • This type of charging causes accumulation of battery polarization.
  • the current used in the charging process is getting larger and larger, which exacerbates the heat generation of the battery, and at the same time, under the effect of the polarization of the battery.
  • the object of the present invention is to overcome the deficiencies of the prior art and provide a secondary battery charging method capable of effectively reducing battery polarization accumulation, reducing battery heat generation, and slowing battery temperature rise.
  • the present invention provides a secondary battery charging method including the following steps:
  • Step one charging the battery with a constant current I1, the charging time is t1;
  • Step 2 discharging the battery with a constant current I2, the discharge time is t2, wherein t2 satisfies 5 ⁇ t1/t2 ⁇ 50;
  • Step 3 repeat steps 1 and 2 until the battery voltage reaches the cutoff voltage V0;
  • step four the battery is charged at a constant voltage V0 until the battery current reaches the off current I3.
  • the constant current I1 and the constant current I2 satisfy the relationship of 2 ⁇ I1/I2 ⁇ 200.
  • the constant current I1 has a value of 0.2 C to 5 C.
  • the value of the charging time t1 is 0.1 s to 30 s.
  • the value of the constant current I2 is 0C to 0.2C.
  • the value of the discharge time t2 is from 0.01 s to 5 s.
  • the value of the cutoff voltage V0 is 3V to 5V.
  • the value of the off current I3 is 0.01 C to 0.1 C.
  • the battery is a lithium ion battery, a lithium metal battery, a lead acid battery, a nickel separator battery, a nickel hydrogen battery, a lithium sulfur battery, a lithium air battery or a sodium ion battery.
  • the method further includes placing the battery The step in the environment of 0 ° C ⁇ 60 ° C, this step is completed before step one.
  • the secondary battery charging method of the present invention has at least the following beneficial technical effects: the charging of the battery is effectively reduced by using a charging method in which a wide positive pulse current and a narrow negative pulse current are spaced apart from each other, It reduces the heat generation of the battery, slows down the temperature rise during battery charging, significantly improves battery performance and user experience, and prevents potential safety hazards caused by battery temperature rise.
  • 1 is a graph showing a charging current of a secondary battery charging method of the present invention.
  • Fig. 2 is a graph showing the charging voltage of the first embodiment of the secondary battery charging method of the present invention.
  • Example 4 is a comparison diagram of charging currents of Example 1 and Comparative Example 1 of the present invention.
  • Figure 5 is a comparison diagram of charging voltages of Example 1 and Comparative Example 1 of the present invention.
  • Figure 6 is a comparison diagram of charging temperatures of Example 1 of the present invention and Comparative Example 1.
  • the secondary battery charging method of the present invention comprises the following steps:
  • Step one charging the battery with a constant current I1, the charging time is t1;
  • Step two discharging the battery with a constant current I2, the discharge time is t2, wherein t2 satisfies 5 ⁇ t1/t2 ⁇ 50;
  • Step 3 repeat steps 1 and 2 until the battery voltage reaches the cutoff voltage V0;
  • step four the battery is charged at a constant voltage V0 until the battery current reaches the off current I3.
  • the battery system used in the examples and the comparative examples is a battery made of LiCoO 2 as a main material of the cathode, graphite as a main material of the anode, a separator, an electrolyte and a package, and a battery formed by assembly, formation and aging.
  • the cathode is composed of 96.7% LiCoO2 (as a cathode active material), 1.7% PVDF (as a binder) and 1.6% SP (as a conductive agent), and the anode is composed of 98% artificial graphite (as an anode active material), 1.0%.
  • SBR as a binder
  • CMC as a thickener
  • the separator is a PP, PE or PP composite membrane.
  • the electrolyte consists of (30% EC + 30% PC + 40% DEC) (as an organic solvent). ), 1 mol/L LiPF6 and (0.5% VC, 5% FEC, 4% VEC) (as an additive). At 25 ° C, the full charge capacity of this battery is 3200 mAh, and the cutoff voltage V0 is 4.4V.
  • Embodiment 1 the specific steps of Embodiment 1 are as follows:
  • Embodiment 2 The specific steps of Embodiment 2 are as follows:
  • Embodiment 3 The specific steps of Embodiment 3 are as follows:
  • Embodiment 4 The specific steps of Embodiment 4 are as follows:
  • Embodiment 5 The specific steps of Embodiment 5 are as follows:
  • Embodiment 6 The specific steps of Embodiment 6 are as follows:
  • Embodiment 7 The specific steps of Embodiment 7 are as follows:
  • Embodiment 8 The specific steps of Embodiment 8 are as follows:
  • Embodiment 9 The specific steps of Embodiment 9 are as follows:
  • Embodiment 10 The specific steps of Embodiment 10 are as follows:
  • Embodiment 11 The specific steps of Embodiment 11 are as follows:
  • Comparative Example 1 Please refer to FIG. 3, the specific steps of Comparative Example 1 are as follows:
  • Comparative Example 2 The specific steps of Comparative Example 2 are as follows:
  • the temperature data of the surface of the battery cell was collected using a Hio LR8431-30 type data recorder.
  • Table 1 lists the temperature rises of the charging process for different examples and comparative examples and the time required to charge to 100% SOC. It can be seen from the table that for the same battery system, the conventional constant current constant voltage charging used with the comparative example Compared with the method, the charging method of the present invention used in the embodiment can reduce the temperature rise during battery charging, and at the same time, can increase the charging speed.
  • the working principle of the charging method of the present invention can be seen by examining the voltage variation during charging. 4, 5, and 6 are current, voltage, and temperature changes in the charging process of Example 1 and Comparative Example 1, respectively. As can be seen from the figure, the voltage rise of Example 1 was slower than that of Comparative Example 1. The charging voltage of Example 1 was less than the charging voltage of Comparative Example 1 during the first 10 minutes of the charging process. This enables the battery of Embodiment 1 to effectively alleviate the polarization accumulation during charging, which in turn reduces the voltage jump caused by polarization, on the one hand reduces the heat generation of the battery, reduces the temperature rise of the battery, and on the other hand extends the large The charging time of the current shortens the charging time of the constant voltage, thereby increasing the charging speed.
  • the constant current I1 and the constant current I2 satisfy the relationship 2 ⁇ I1/I2 ⁇ 200.
  • the constant current I1 is from 0.2 C to 5 C.
  • the charging time t1 is from 0.1 s to 20 s.
  • the constant current I2 is from 0C to 0.2C.
  • the discharge time t2 is from 0.01 s to 2 s.
  • the cut-off voltage V0 is between 3V and 5V.
  • the off current I3 is from 0.01 C to 0.1 C.
  • the charging ambient temperature is between 0 ° C and 60 ° C.
  • the charging method of the present invention will have a more excellent technical effect.
  • the charging method of the present invention can be implemented by integrating a charging circuit into a battery charger, a battery adapter, a battery control circuit, and an integrated chip, and is applied to a mobile phone, a notebook computer, a tablet computer, a music player, a Bluetooth headset,
  • suitable secondary battery systems include lithium ion batteries, lithium metal batteries, lead acid batteries, and nickel. Battery, nickel-metal hydride battery, lithium-sulfur battery, lithium air battery, sodium ion battery, etc.
  • the advantageous technical effects of the secondary battery charging method of the present invention include, but are not limited to, charging by using a wide positive pulse current and a narrow negative pulse current, respectively, with respect to the prior art.
  • the method effectively reduces the accumulation of battery polarization, reduces the heat generation of the battery, slows down the temperature rise during battery charging, prevents the safety hazard caused by the battery temperature rise, and also increases the charging speed, significantly improving the battery performance and user experience.

Abstract

一种二次电池充电方法，其包括：以恒定电流I1对电池充电，充电时间为t1；以恒定电流I2对电池放电，放电时间为t2，其中，t2满足5≤t1/t2≤50；重复上述的充电和放电步骤，直至电池电压达到截止电压V0；以恒定电压V0对电池充电，直至电池电流达到截止电流I3。所述充电方法通过使用宽的正脉冲电流和窄的负脉冲电流互相间隔的充电方式进行充电，有效减少了电池极化的积累，降低了电池的产热，减缓了电池充电过程中的温升，显著改善了电池性能和用户体验，防止电池温升造成的安全隐患。

Description

二次电池充电方法 技术领域
本发明属于电池技术领域，更具体地说，本发明涉及一种二次电池充电方法。
背景技术
二次电池充电时，电池自身存在的内阻以及充电造成的极化积累等因素，导致其在充电过程中持续产热、温度升高。
为了解决二次电池充电时的温升问题，多年来研究人员通过对电池材料、电池结构进行改进以降低电池内阻，从而降低温升，但这同时也造成电池成本提高的问题，而且增加了相关工艺的复杂度。
而以电池充电的极化积累作为切入点，在不改变电池原有配方和结构的基础上，通过改变充电条件，也能对二次电池充电过程中的温升问题产生一定的优化效果。目前，二次电池的充电方式为：使用恒定电流对电池持续充电至某一电位，再在此电位对电池进行恒压充电。这种充电方式会造成电池极化的积累。特别是随着当前快速充电技术的兴起，为了提高二次电池的充电速度，充电过程中所使用的电流越来越大，这加剧了电池的产热，同时，在电池极化增长的作用下，电池温度急剧上升，不但影响便携式设备的使用体验，更可能影响电池性能、带来安全隐患。
有鉴于此，有必要提供一种能够解决上述问题的二次电池充电方法。
发明内容
本发明的目的在于：克服现有技术的不足，提供一种能够有效减少电池极化积累、降低电池产热、减缓电池温升的二次电池充电方法。
为了实现上述发明目的，本发明提供一种二次电池充电方法，其包括以下步骤：
步骤一，以恒定电流I1对电池充电，充电时间为t1；
步骤二，以恒定电流I2对电池放电，放电时间为t2，其中，t2满足5≤t1/t2≤50；
步骤三，重复步骤一和步骤二，直至电池电压达到截止电压V0；
步骤四，以恒定电压V0对电池充电，直至电池电流达到截止电流I3。
作为本发明二次电池充电方法的一种改进，所述恒定电流I1与恒定电流I2满足关系2≤I1/I2≤200。
作为本发明二次电池充电方法的一种改进，所述恒定电流I1的数值为0.2C～5C。
作为本发明二次电池充电方法的一种改进，所述充电时间t1的数值为0.1s～30s。
作为本发明二次电池充电方法的一种改进，所述恒定电流I2的数值为0C～0.2C。
作为本发明二次电池充电方法的一种改进，所述放电时间t2的数值为0.01s～5s。
作为本发明二次电池充电方法的一种改进，所述截止电压V0的数值为3V～5V。
作为本发明二次电池充电方法的一种改进，所述截止电流I3的数值为0.01C～0.1C。
作为本发明二次电池充电方法的一种改进，所述电池为锂离子电池、锂金属电池、铅酸电池、镍隔电池、镍氢电池、锂硫电池、锂空气电池或钠离子电池。
作为本发明二次电池充电方法的一种改进，所述方法还包括将电池置于 0℃～60℃环境中的步骤，此步骤在步骤一之前完成。
与现有技术相比，本发明二次电池充电方法至少具有以下有益的技术效果：通过使用宽的正脉冲电流和窄的负脉冲电流互相间隔的充电方式，有效减少了电池极化的积累，降低了电池的产热，减缓了电池充电过程中的温升，显著改善了电池性能和用户体验，防止电池温升造成的安全隐患。
附图说明
下面结合附图和具体实施方式，对本发明二次电池充电方法及其有益技术效果进行详细说明。
图1为本发明二次电池充电方法的充电电流的曲线图。
图2为本发明二次电池充电方法实施例1的充电电压的曲线图。
图3为本发明二次电池充电方法对比例1的充电电流的曲线图。
图4为本发明实施例1与对比例1的充电电流的对比图。
图5为本发明实施例1与对比例1的充电电压的对比图。
图6为本发明实施例1与对比例1的充电温度的对比图。
具体实施方式
为了使本发明的发明目的、技术方案和技术效果更加清晰明白，以下结合附图和具体实施方式，对本发明进行进一步详细说明。应当理解的是，本说明书中描述的具体实施方式仅仅是为了解释本发明，并不是为了限定本发明。
请参阅图1所示，本发明二次电池充电方法包括以下步骤：
步骤一，以恒定电流I1对电池充电，充电时间为t1；
步骤二，以恒定电流I2对电池放电，放电时间为t2，其中t2满足5≤t1/t2≤50；
步骤三，重复步骤一和步骤二，直至电池电压达到截止电压V0；
步骤四，以恒定电压V0对电池充电，直至电池电流达到截止电流I3。
以下为本发明二次电池充电方法的实施例和对比例。
实施例与对比例所采用的电池体系是以LiCoO2作为阴极主要材料，以石墨作为阳极主要材料，再加上隔膜、电解液及包装壳，通过组装、化成及陈化等工艺所制成的电池。其中，阴极由96.7％LiCoO2(作为阴极活性物质)、1.7％PVDF(作为粘结剂)和1.6％SP(作为导电剂)混合组成，阳极由98％人造石墨(作为阳极活性物质)、1.0％SBR(作为粘结剂)和1.0％CMC(作为增稠剂)混合组成，隔膜为PP、PE或PP复合膜，电解液由(30％EC+30％PC+40％DEC)(作为有机溶剂)、1mol/L LiPF6和(0.5％VC、5％FEC、4％VEC)(作为添加剂)组成。25℃时，此电池的满充充电容量为3200mAh，截止电压V0为4.4V。
实施例1
请参阅图2所示，实施例1的具体步骤如下：
1)将电池置于25℃环境中；
2)以恒定电流5C对电池充电，充电时间为0.9s；
3)以恒定电流0.1C对电池放电，放电时间为0.1s；
4)重复步骤2)～3)直到电池电压达到4.4V；
5)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
实施例2
实施例2的具体步骤如下：
1)将电池置于25℃环境中；
2)以恒定电流5C对电池充电，充电时间为0.1s；
3)以恒定电流0.2C对电池放电，放电时间为0.01s；
4)重复步骤2)～3)直到电池电压达到4.4V；
5)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
实施例3
实施例3的具体步骤如下：
1)将电池置于25℃环境中；
2)以恒定电流5C对电池充电，充电时间为20s；
3)以恒定电流0.2C对电池放电，放电时间为0.2s；
4)重复步骤2)～3)直到电池电压达到4.4V；
5)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
实施例4
实施例4的具体步骤如下：
1)将电池置于25℃环境中；
2)以恒定电流2C对电池充电，充电时间为30s；
3)以恒定电流0.1C对电池放电，放电时间为5s；
4)重复步骤2)～3)直到电池电压达到4.4V；
5)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
实施例5
实施例5的具体步骤如下：
1)将电池置于25℃环境中；
2)以恒定电流2C对电池充电，充电时间为1s；
3)以恒定电流0.02C对电池放电，放电时间为0.05s；
4)重复步骤2)～3)直到电池电压达到4.4V；
5)以恒定电压4.4V对电池充电，直到电池电流达到0.01C。
实施例6
实施例6的具体步骤如下：
1)将电池置于25℃环境中；
2)以恒定电流0.7C对电池充电，充电时间为5s；
3)以恒定电流0C对电池放电，放电时间为1s；
4)重复步骤2)～3)直到电池电压达到4.4V；
5)以恒定电压4.4V对电池充电，直到电池电流达到0.1C。
实施例7
实施例7的具体步骤如下：
1)将电池置于25℃环境中；
2)以恒定电流0.7C对电池充电，充电时间为3s；
3)以恒定电流0.1C对电池放电，放电时间为0.5s；
4)重复步骤2)～3)直到电池电压达到4.4V；
5)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
实施例8
实施例8的具体步骤如下：
1)将电池置于0℃环境中；
2)以恒定电流0.2C对电池充电，充电时间为0.9s；
3)以恒定电流0.02C对电池放电，放电时间为0.1s；
4)重复步骤2)～3)直到电池电压达到4.4V；
5)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
实施例9
实施例9的具体步骤如下：
1)将电池置于10℃环境中；
2)以恒定电流0.5C对电池充电，充电时间为0.1s；
3)以恒定电流0.02C对电池放电，放电时间为0.01s；
4)重复步骤2)～3)直到电池电压达到4.4V；
5)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
实施例10
实施例10的具体步骤如下：
1)将电池置于40℃环境中；
2)以恒定电流3C对电池充电，充电时间为10s；
3)以恒定电流0.1C对电池放电，放电时间为0.5s；
4)重复步骤2)～3)直到电池电压达到4.4V；
5)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
实施例11
实施例11的具体步骤如下：
1)将电池置于60℃环境中；
2)以恒定电流1C对电池充电，充电时间为5s；
3)以恒定电流0.05C对电池放电，放电时间为0.1s；
4)重复步骤2)～3)直到电池电压达到4.4V；
5)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
对比例1
请参阅图3，对比例1的具体步骤如下：
1)将电池置于25℃环境中；
2)以恒定电流5C对电池充电，直到电池电压达到4.4V；
3)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
对比例2
对比例2的具体步骤如下：
1)将电池置于25℃环境中；
2)以恒定电流2C对电池充电，直到电池电压达到4.4V；
3)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
对比例3
对比例3的具体步骤如下：
1)将电池置于25℃环境中；
2)以恒定电流0.7C对电池充电，直到电池电压达到4.4V；
3)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
对比例4
对比例4的具体步骤如下：
1)将电池置于0℃环境中；
2)以恒定电流0.2C对电池充电，直到电池电压达到4.4V；
3)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
对比例5
对比例5的具体步骤如下：
1)将电池置于10℃环境中；
2)以恒定电流0.5C对电池充电，直到电池电压达到4.4V；
3)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
对比例6
对比例6的具体步骤如下：
1)将电池置于40℃环境中；
2)以恒定电流3C对电池充电，直到电池电压达到4.4V；
3)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
对比例7
对比例7的具体步骤如下：
1)将电池置于60℃环境中；
2)以恒定电流1C对电池充电，直到电池电压达到4.4V；
3)以恒定电压4.4V对电池充电，直到电池电流达到0.05C。
为了检验本发明二次电池充电方法的技术效果，在实施例和对比例的电池充电过程中，使用日置LR8431-30型数据记录仪采集电芯表面的温度数据。表1列出了不同的实施例与对比例的充电过程温升情况以及充电到100％SOC所需要的时间。由表可见，对于同一电池体系，与对比例使用的传统恒流恒压充电 方法相比，实施例使用的本发明充电方法可以降低电池充电过程中的温升，同时还能够提高充电速度。
表1、实施例与对比例的充电参数和充电效果对比
Figure PCTCN2016098448-appb-000001
通过考察充电过程中的电压变化，可以看出本发明充电方法的工作原理。图4、图5和图6分别为实施例1和对比例1在充电过程中的电流、电压、温度变化曲线。由图可见，相对于对比例1，实施例1的电压上升更为缓慢。在充电过程的前10min内，实施例1的充电电压均小于对比例1的充电电压。这使得实施例1的电池能够有效缓解充电过程中的极化积累，反过来降低由极化带来的电压跳跃，一方面减少了电池产热，降低了电池温升；另一方面延长了大电流充电的时间，缩短了恒压充电的时间，从而提高充电速度。
根据本发明的一个优选实施方式，恒定电流I1与恒定电流I2满足关系2≤I1/I2≤200。
根据本发明的一个优选实施方式，恒定电流I1为0.2C～5C。
根据本发明的一个优选实施方式，充电时间t1为0.1s～20s。
根据本发明的一个优选实施方式，恒定电流I2为0C～0.2C。
根据本发明的一个优选实施方式，放电时间t2为0.01s～2s。
根据本发明的一个优选实施方式，截止电压V0为3V～5V。
根据本发明的一个优选实施方式，截止电流I3为0.01C～0.1C。
根据本发明的一个优选实施方式，充电环境温度为0℃～60℃。
在优选参数条件下，本发明的充电方法将具有更优良的技术效果。
需要说明的是，本发明的充电方法可以通过充电电路集成于电池充电器、电池适配器、电池控制电路、集成芯片中实现，并应用于手机、笔记本电脑、平板电脑、音乐播放器、蓝牙耳机、移动电源、其他便携式手持设备、电动工具、无人机、电动车等电子产品和设备的动力或储能电池上，适用的二次电池体系包括锂离子电池、锂金属电池、铅酸电池、镍隔电池、镍氢电池、锂硫电池、锂空气电池、钠离子电池等。
结合以上对本发明的详细描述可以看出，相对于现有技术，本发明二次电池充电方法的有益技术效果包括但不限于：通过使用宽的正脉冲电流和窄的负脉冲电流互相间隔的充电方式，有效减少了电池极化的积累，降低了电池的产热，减缓了电池充电过程中的温升，防止电池温升造成的安全隐患，同时还提高了充电速度，显著改善了电池性能和用户体验。
根据上述原理，本发明还可以对上述实施方式进行适当的变更和修改。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。

Claims (10)

  1. 一种二次电池充电方法，其特征在于：所述方法包括以下步骤：
    步骤一，以恒定电流I1对电池充电，充电时间为t1；
    步骤二，以恒定电流I2对电池放电，放电时间为t2，其中，t2满足5≤t1/t2≤50；
    步骤三，重复步骤一和步骤二，直至电池电压达到截止电压V0；
    步骤四，以恒定电压V0对电池充电，直至电池电流达到截止电流I3。
  2. 根据权利要求1所述的二次电池充电方法，其特征在于：所述恒定电流I1与恒定电流I2满足关系2≤I1/I2≤200。
  3. 根据权利要求1所述的二次电池充电方法，其特征在于：所述恒定电流I1的数值为0.2C～5C。
  4. 根据权利要求1所述的二次电池充电方法，其特征在于：所述充电时间t1的数值为0.1s～30s。
  5. 根据权利要求1所述的二次电池充电方法，其特征在于：所述恒定电流I2的数值为0C～0.2C。
  6. 根据权利要求1所述的二次电池充电方法，其特征在于：所述放电时间t2的数值为0.01s～5s。
  7. 根据权利要求1所述的二次电池充电方法，其特征在于：所述截止电压V0的数值为3V～5V。
  8. 根据权利要求1所述的二次电池充电方法，其特征在于：所述截止电流I3的数值为0.01C～0.1C。
  9. 根据权利要求1所述的二次电池充电方法，其特征在于：所述电池为锂离子电池、锂金属电池、铅酸电池、镍隔电池、镍氢电池、锂硫电池、锂空气电池或者钠离子电池。
  10. 根据权利要求1所述的二次电池充电方法，其特征在于：所述方法还包括将电池置于0℃～60℃环境中的步骤，此步骤在步骤一之前完成。
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