WO2016178147A1

WO2016178147A1 - Lithium battery assembly capable of providing high discharge pulse within wide temperature range, and forming method

Info

Publication number: WO2016178147A1
Application number: PCT/IB2016/052524
Authority: WO
Inventors: 王然石; 徐禎祥; 黎胜
Original assignee: 朗陞科技集团(香港)有限公司
Priority date: 2015-05-06
Filing date: 2016-05-04
Publication date: 2016-11-10
Also published as: HK1203296A2; CN105390775A; CN106229587A

Abstract

Disclosed is a rechargeable secondary lithium ion battery, having an improved anode material, cathode material and electrolyte solution, so as to reduce the formation of dendrites by deposits of lithium metal on the surface of carbonaceous material when lithium ions are inserted into the carbonaceous material during charging, and mitigate the risk of side reactions. Also disclosed are a lithium battery assembly capable of providing a high discharge pulse within a wide temperature range, and a forming method. The lithium battery assembly comprises a primary lithium/oxyhalide battery and a rechargeable secondary lithium ion battery connected in parallel to the primary lithium/oxyhalide battery, the open circuit voltage of the rechargeable secondary lithium ion battery in a full state being higher than that of the primary lithium/oxyhalide battery connected in parallel. Since the open circuit voltage of the rechargeable secondary lithium ion battery in the full state is higher than that of the primary lithium/oxyhalide battery connected in parallel, the rechargeable secondary lithium ion battery is lower than the full state when the two batteries are connected in parallel and under a load end open circuit condition, thereby alleviating ageing and self-discharging caused by side reactions.

Description

可于宽温度范围提供高放电脉冲的锂电池組件及形成方法技术领域 Lithium battery assembly capable of providing high discharge pulse over a wide temperature range and method of forming the same

本发明涉及锂电池技术领域，尤其涉及一种可于宽温度范围提供高放电脉冲的锂电池组件及形成方法。背景技术 The present invention relates to the field of lithium battery technology, and more particularly to a lithium battery assembly and a method for forming a high discharge pulse that can provide a wide temperature range. Background technique

随着无线通讯技术的快速发展，移动设备已经全面数字化而功能也日趋复杂。相应的，设备工作模式对电源的需求转为瞬时大电流脉冲用于传输无线数据。以全球移动通信*** （GSM) 为例，其典型需求为 2A、 500ms脉冲电流。另以近年快速发展的智能抄表（AMR) ***为例，其具有自动采集数字化水表、电表读数能力，通过无线通讯定期将数据传输至移动收集终端，并进一步上传中央管理平台。应用于此类 AMR***的电源应具备长寿命、瞬时大电流放电、以及因应户外条件的宽工作温高度范围的能力。 With the rapid development of wireless communication technology, mobile devices have been fully digitized and their functions have become increasingly complex. Correspondingly, the demand for power in the device operating mode is converted to an instantaneous high current pulse for transmitting wireless data. Taking the Global System for Mobile Communications (GSM) as an example, its typical demand is 2A, 500ms pulse current. Taking the rapid development of the intelligent meter reading (AMR) system in recent years as an example, it has the ability to automatically collect digital water meters and meter readings, and periodically transmit data to mobile collection terminals via wireless communication, and further upload the central management platform. Power supplies used in such AMR systems should have long life, instantaneous high current discharge, and the ability to accommodate a wide range of operating temperature ranges for outdoor conditions.

在传统的移动设备单电池电源***中，锂 /(¾氧化物一次电化学电池例如锂 / 亚疏酰氯（Li/SOCl₂) 或锂 /疏酰氯（Li/S0₂Cl₂) 电池以其高能量密度、长使用寿命、和相对宽的工作温度范围，可作为一类重要的解决方案。此类***典型的用电需求，一般包括一个低至数毫安级的持续背景电流，和间歇性的数十毫安至数安培级的短电流脉冲，其中脉冲宽度在毫秒级别。然而，在开路或低电流条件下，锂 /(¾氧化物电池的阳极会在表面形成钝化层，严重降低电池的可用工作电流。在此情况下，高电流放电脉冲会导致电池输出电压急剧下降至较低水平，而不能驱动相应的用电器件。通过在电池电解^中加入添加剂，例如聚氯乙烯（Polyvinyl Chloride)、三氧化疏（S0₃)，可提升钝化层电导率而部分改善相关问题，但钝化过程依然存在。同时添加剂效果会随时间在数月内减弱，相对于此类电池数年的工作寿命，对整体电池性能提升有限。另外的可能解决方式包括改变电池结构设计从碳包式（Bobbin) 至卷绕式（Jelly-Roll) , 以获得更大的电极表面积从而提升放电功率。然而此方式不仅不能解决电极钝化问题，电池在特定条件下，例如短路、挤压、穿刺等，存在较高的***风险。 In a conventional mobile device single-cell power system, a lithium/(3⁄4 oxide primary electrochemical cell such as lithium/succinyl chloride (Li/SOCl ₂ ) or lithium/oacyl chloride (Li/S0 ₂ Cl ₂ ) cells is high Energy density, long life, and a relatively wide operating temperature range can be an important solution. Typical power requirements for such systems typically include a continuous background current as low as a few milliamps, and intermittent Short-current pulses of tens of milliamperes to amps, where the pulse width is on the order of milliseconds. However, under open or low current conditions, the anode of lithium/(3⁄4 oxide cells) forms a passivation layer on the surface, which is severely reduced. The available operating current of the battery. In this case, the high current discharge pulse causes the battery output voltage to drop sharply to a lower level, and cannot drive the corresponding consumer. By adding an additive such as polyvinyl chloride to the battery. Polyvinyl Chloride), trioxide (S0 ₃ ), can improve the conductivity of the passivation layer and partially improve related problems, but the passivation process still exists. Attenuated over time in a few months, compared to the battery's working life for several years, there is limited overall battery performance improvement. Other possible solutions include changing the battery structure design from Bobbin to winding (Jelly- Roll) to obtain a larger electrode surface area to increase the discharge power. However, this method can not only solve the problem of electrode passivation, and the battery has a high risk of explosion under certain conditions, such as short circuit, extrusion, puncture and the like.

关于其它解决方案，本领域已知将具有高放电功率的电容器件与一次电化学电池并联的组合，用以提高瞬间放电的能力。其中一种前例电路 1简图如图 1 所示，包括一个一次电化学电池 2，以及与之并联的电容器件 3。这种方式能够一定程度上减低两接入端 4、 5间进行大电流放电时的电压降问题。电路 1典型的工作方式为电容器 3由一次电池 2充电至两者电压相等。当接入端 4、 5间开路时一次电池 2提供小电流予电容器 3以补偿其漏电流。当接入端 4、 5间接入负载而需要电路 1提供大电流时，部分电流可由电容器 3输出从而降低了对一次电池 2的电流需求。因此在电容器 3可放电容量内，一次电池 2因高电流放电导致的低电压输出问题可以减轻。 With regard to other solutions, it is known in the art to combine a capacitive device having a high discharge power in parallel with a primary electrochemical cell to increase the ability to instantaneously discharge. A schematic diagram of one of the preceding examples of circuit 1 is shown in Figure 1, including a primary electrochemical cell 2, and a capacitive device 3 connected in parallel therewith. In this way, the voltage drop problem during high current discharge between the two access terminals 4 and 5 can be reduced to some extent. Circuit 1 typical The mode of operation is that the capacitor 3 is charged by the primary battery 2 until the voltages of the two are equal. When the access terminals 4, 5 are open, the primary battery 2 provides a small current to the capacitor 3 to compensate for its leakage current. When the access terminals 4, 5 are connected to the load and the circuit 1 is required to supply a large current, a part of the current can be output from the capacitor 3 to lower the current demand on the primary battery 2. Therefore, within the discharge capacity of the capacitor 3, the problem of low voltage output of the primary battery 2 due to high current discharge can be alleviated.

然而，上述方案可应用范围较小。主要原因为：若維持电容器件 3 电压在负载工作周期内的电压在特定水平，考虑到前述通讯器件所需脉冲能量，要求电容器 3 具有极大电容值。而典型的具有极大电容值的电容器对于绝大多数应用来说，其成本过于昂贵以及体积不可接受。 However, the above scheme can be applied in a small range. The main reason is: If the voltage of the capacitor device 3 voltage is maintained at a specific level during the duty cycle of the load, the capacitor 3 is required to have a maximum capacitance value in consideration of the pulse energy required for the aforementioned communication device. Typical capacitors with very large capacitance values are too expensive and unacceptable for most applications.

前例 WO专利 2007097534 (Chung Se-II等人）将上述电容器件 3替换为双电层电容（Electric Double-Layer Capacitor, EDLC) 或超级电容。超级电容具有远高于常见电解电容器的电容值（同体积条件下典型值为电解电容数百倍），因而可以部分减低因电容体积庞大导致的实用性问题。然而此类替换不能解决漏电流的问题。超级电容器因其高自放电率导致的容量损失可达 50%/月，远高于一般锂离子电池的 5%/月（Danilo Porcarelli等， Networked Sensing Systems (INSS 2012 Ninth International Conference on, pages 1 -4,2012 )。考虑到超级电容器的高电容值和相应的高储电能力，其开路条件下相对较大的漏电损失会严重消耗与之配合的一次电池容量，而影响电源的工作寿命。 The former example WO Patent 2007097534 (Chung Se-II et al.) replaces the above-mentioned capacitor device 3 with an Electric Double-Layer Capacitor (EDLC) or a super capacitor. Supercapacitors have much higher capacitance than common electrolytic capacitors (typically hundreds of times the electrolytic capacitors under the same volume), which can partially reduce the practical problems caused by the large capacitance. However, such replacement does not solve the problem of leakage current. Supercapacitors can lose up to 50%/month due to their high self-discharge rate, which is much higher than 5%/month for general lithium-ion batteries (Danilo Porcarelli et al., Networked Sensing Systems (INSS 2012 Ninth International Conference on, pages 1 - 4, 2012) Considering the high capacitance value of the supercapacitor and the corresponding high storage capacity, the relatively large leakage loss under the open circuit condition will seriously consume the primary battery capacity, which affects the working life of the power supply.

US专利 8,119,276 (Arden P. Johnson等人）描述了述了一种并联一次锂 /卤氧化物电池和二次锂离子电池的复合电源***。二次电池代替电容器件可以改善通讯应用中放电容量不足的问题。然而，其电源***特別限定"二次电池在完全充满状态下较全新一次电化学电池开路电压低约 0.05V至约 0.8V"。因而此前例中的可充电二次电池在所述电源中有过充的风险，而导致电解液分解或短路等安全问题。虽然所述复合电源***可包含串联于一次电池和二次电池之间的二极管元件以保护二次电池。由于二极管两端电压降会随时间及使用条件变化，因此问题并未完全解决。另外在所述前例理想条件下，其中锂离子二次电池在电源无负载情况下处于被一次电池充满或略微过充的状态。而锂离子电池在充满或过充状态下阳极表面极化较强，从而更易发生副反应而导致漏电以及容量损失，最终縮短电池***的使用寿命。 U.S. Patent 8,119,276 (Arden P. Johnson et al.) describes a composite power supply system for a parallel primary lithium/halide oxide battery and a secondary lithium ion battery. Replacing the capacitor device with a secondary battery can improve the problem of insufficient discharge capacity in communication applications. However, its power supply system is particularly limited to "the secondary battery is nearly 0.05V to about 0.8V lower than the new electrochemical cell open circuit voltage in a fully charged state." Therefore, the rechargeable secondary battery in the prior art has a risk of overcharging in the power source, resulting in safety problems such as decomposition or short circuit of the electrolyte. Although the composite power supply system may include a diode element connected in series between the primary battery and the secondary battery to protect the secondary battery. Since the voltage drop across the diode changes over time and usage conditions, the problem is not completely solved. Further, under the above-mentioned ideal conditions, the lithium ion secondary battery is in a state of being filled or slightly overcharged by the primary battery under no load of the power source. However, when the lithium ion battery is fully charged or overcharged, the anode surface is strongly polarized, so that side reactions are more likely to occur, resulting in leakage and capacity loss, and finally shortening the service life of the battery system.

US专利 5,998,052 (Yamin等人）描述了一种包含一次电池和二次可充电电池的复合电源***。同样的，二次电池代替电容器件可以改善通讯应用中放电容量不足的问题。然而其中一次电池及二次电池的组合方式限于：二次电池置于一次电池中、一次电池置于二次电池中、以及一次电池与二次电池在印刷电路板上以导电连接并联。这种设计使得所述复合电池***制造过程复杂以及成本较高。同时令其中任意一个电池不能正常工作时元件更换困难，而进一步提高应用中的維护成本。其外，所述前例中对二次锂离子电池的结构并无限制。考虑到锂离子电池的较差低温性能（典型工作温度〉 -10°C )，此类复合电池电源在户外通讯以及智能抄表***等领域中的应用有限。发明内容 No. 5,998,052 (Yamin et al.) describes a composite power supply system comprising a primary battery and a secondary rechargeable battery. Similarly, replacing the capacitor with a secondary battery can improve the problem of insufficient discharge capacity in communication applications. However, the combination of the primary battery and the secondary battery is limited to: the secondary battery is placed in the primary battery, the primary battery is placed in the secondary battery, and the primary battery and the secondary battery are printed. The boards are connected in parallel by conductive connections. This design makes the composite battery system manufacturing process complicated and costly. At the same time, it is difficult to replace components when any one of the batteries is not working properly, and the maintenance cost in the application is further improved. Further, the structure of the secondary lithium ion battery in the above example is not limited. Considering the poor low temperature performance of lithium-ion batteries (typical operating temperature > -10 ° C), such composite battery power supplies are limited in applications such as outdoor communication and smart meter reading systems. Summary of the invention

本发明的实施方案提供一种基于前例的改进型复合电源***，即锂电池组件，该锂电池组件可于宽温度范围提供高放电脉冲，还提供该锂电池组件的形成方法。 An embodiment of the present invention provides an improved composite power supply system based on the foregoing example, that is, a lithium battery assembly that can provide a high discharge pulse over a wide temperature range, and a method of forming the lithium battery assembly.

根据本发明的第一方面，本发明提供一种可充电二次锂离子电池，其具有改进的阳极材料、阴极材料和电解液，使得该二次锂离子电池的各种特性都有很大的改善和提高。具体而言，所述的可充电二次锂离子电池中包含阴极材料和阳极复合碳^材料，上述阴极材料可逆地结合锂离子的容量与上述阳极复合碳^材料以 LiC6形式可逆地结合锂离子的容量之比在 0.5:1至 2:1之间，以减轻充电过程中锂离子***碳^材料时锂金属在其表面的沉积形成枝晶以及发生副反应的风险。 According to a first aspect of the present invention, there is provided a rechargeable secondary lithium ion battery having an improved anode material, a cathode material and an electrolyte such that various characteristics of the secondary lithium ion battery are large Improve and improve. Specifically, the rechargeable secondary lithium ion battery includes a cathode material and an anode composite carbon material, wherein the cathode material reversibly combines the capacity of the lithium ions and the anode composite carbon material reversibly binds the lithium ion in the form of LiC6. The ratio of the capacity is between 0.5:1 and 2:1 to reduce the risk of lithium metal depositing on the surface of the lithium metal during the charging process to form dendrites and side reactions.

根据本发明的另一方面，本发明提供一种可于宽温度范围提供高放电脉冲的锂电池组件，该锂电池组件包括一个或多个一次锂 / (¾氧化物电池以及与其并联的可充电二次锂离子电池；特别的，其中可充电二次锂离子电池充满状态下的开路电压高于并联的上述一次锂 /(¾氧化物电池的开路电压，从而使两者并联且负载端开路条件下可充电二次锂离子电池的电压低于充满状态的电压，以减轻老化以及副反应导致的自放电现象。 According to another aspect of the present invention, there is provided a lithium battery pack that can provide a high discharge pulse over a wide temperature range, the lithium battery pack including one or more primary lithium / (3⁄4 oxide cells and rechargeable in parallel therewith) a secondary lithium ion battery; in particular, wherein the open circuit voltage in the fully charged state of the rechargeable secondary lithium ion battery is higher than the open circuit voltage of the above-mentioned primary lithium/(3⁄4 oxide battery) in parallel, thereby making the two parallel and the open end conditions of the load end The voltage of the lower rechargeable secondary lithium ion battery is lower than the voltage of the full state to reduce self-discharge caused by aging and side reactions.

作为本发明的进一步改进的实施方案，上述可充电二次锂离子电池中包含阴极材料和阳极复合碳^材料，上述阴极材料可逆地结合锂离子的容量与上述阳极复合碳^材料以 LiC 式可逆地结合锂离子的容量之比在 0.5: 1至 2:1之间，以减轻充电过程中锂离子***碳^材料时锂金属在其表面的沉积形成枝晶以及发生副反应的风险。 As a further improved embodiment of the present invention, the above rechargeable secondary lithium ion battery comprises a cathode material and an anode composite carbon material, wherein the capacity of the cathode material reversibly binding lithium ions and the anode composite carbon material are reversible by LiC type The ratio of the combined lithium ion capacity is between 0.5:1 and 2:1 to reduce the risk of lithium metal depositing on the surface of the lithium metal during the charging process to form dendrites and side reactions.

根据本发明的又一方面，本发明提供一种形成第一方面所述的锂电池组件的方法，该方法包括将按照应用需求计算类型容量的一次锂 /(¾氧化物电池及可充电二次锂离子电池进行并联，其中根据所选择的一次锂 /(¾氧化物电池类型，选择可充电二次锂离子电池充满状态下的开路电压高于并联的一次锂 /(¾氧化物电池的开路电压，使两者并联且负载端开路条件下可充电二次锂离子电池的电压低于充满状态下的电压。 According to still another aspect of the present invention, there is provided a method of forming the lithium battery assembly of the first aspect, the method comprising calculating a primary lithium/(3⁄4 oxide battery and a chargeable secondary) of a type capacity according to an application requirement Lithium-ion batteries are connected in parallel, according to the selected primary lithium/(3⁄4 oxide battery type, the open circuit voltage in the full state of the rechargeable secondary lithium-ion battery is higher than the primary lithium/parallel in parallel (3⁄4 oxide battery) , the electricity of the rechargeable lithium secondary battery can be charged in parallel and the load is open The voltage is lower than the voltage in the full state.

作为本发明的进一步改进的实施方案，上述方法还包括调整可充电二次锂离子电池中阴极材料和阳极复合碳^材料的比例，使得上述阴极材料可逆地结合锂离子的容量与上述阳极复合碳^材料以 LiC₆形式可逆地结合锂离子的容量之比在 0.5:1至 2:1之间。 As a further improved embodiment of the present invention, the method further includes adjusting a ratio of the cathode material and the anode composite carbon material in the rechargeable secondary lithium ion battery such that the cathode material reversibly combines the capacity of the lithium ion with the anode composite carbon The ratio of the capacity of the material to reversibly bind lithium ions in the form of LiC ₆ is between 0.5:1 and 2:1.

本发明的实施方案提供的锂电池组件，由于可充电二次锂离子电池充满状态下的开路电压高于并联的一次锂 /(¾氧化物电池的开路电压，从而使两者并联且负载端开路条件下可充电二次锂离子电池的电压低于充满状态的电压，从而减轻老化以及副反应导致的自放电现象。 According to the embodiment of the present invention, the open circuit voltage in the full state of the rechargeable secondary lithium ion battery is higher than the open circuit voltage of the primary lithium/parallel lithium battery in parallel, so that the two are connected in parallel and the load end is open. Under the condition, the voltage of the rechargeable secondary lithium ion battery is lower than the voltage of the full state, thereby reducing the self-discharge phenomenon caused by aging and side reactions.

此外，在进一步改进的实施方案中，由于阴极材料可逆地结合锂离子的容量与阳极复合碳^材料以 LiC₆形式可逆地结合锂离子的容量之比在 0.5:1至 2:1 之间，从而减轻充电过程中锂离子***碳^材料时锂金属在其表面的沉积形成枝晶以及发生副反应的风险。附图说明 Further, in a further modified embodiment, the ratio of the capacity of the cathode material reversibly binding lithium ions to the capacity of the anode composite carbon material to reversibly bind the lithium ions in the form of LiC ₆ is between 0.5:1 and 2:1, Thereby, the deposition of lithium metal on the surface of the lithium metal into the carbon material during charging is reduced to form dendrites and the risk of side reactions occurs. DRAWINGS

图 1是现有技术描述的电路设计示意图，包括并联的一次电池及电容组合；图 2 是本发明的一个实施方案的锂电池组件的电路设计示意图，包括一次电化学电池以及与之并联的二次可充电锂离子电池； 1 is a schematic diagram of a circuit design described in the prior art, including a primary battery and a capacitor combination in parallel; FIG. 2 is a schematic diagram of a circuit design of a lithium battery assembly according to an embodiment of the present invention, including a primary electrochemical cell and a second parallel thereto Secondary rechargeable lithium ion battery;

图 3 是本发明的一个实施方案的锂电池组件中，可充电二次锂离子电池的电极叠成部分的示意性截面视图； Figure 3 is a schematic cross-sectional view showing an electrode stack portion of a rechargeable secondary lithium ion battery in a lithium battery module according to an embodiment of the present invention;

图 4 是本发明的一个实施例中，可充电二次锂离子电池的充放电电压与容量关系曲线； Figure 4 is a graph showing the relationship between charge and discharge voltage and capacity of a rechargeable secondary lithium ion battery in one embodiment of the present invention;

图 5是本发明的一个实施例中，可充电二次锂离子电池在 -40°C温度下以 7C 倍率放电的电压与时间曲线，并与相同条件下同样容量的商业锂离子电池做比较； 5 is a voltage versus time curve of a rechargeable secondary lithium ion battery discharged at a temperature of -40 ° C at a rate of 7 C in one embodiment of the present invention, and compared with a commercial lithium ion battery of the same capacity under the same conditions;

图 6所示为本发明的一个实施例中，在 -40°C-85°C的温度下，本发明的可充电二次锂离子电池单独放电 350mA 放电电流的曲线图；以及 Figure 6 is a graph showing the discharge current of a 350 mA discharge current of the rechargeable secondary lithium ion battery of the present invention at a temperature of -40 ° C to 85 ° C in an embodiment of the present invention;

图 7所示为本发明的一个实施例中，在 -40°C-85°C的温度下，本发明的一次电池和二次电池并联形成的电池组件的脉冲放电数据曲线图。具体实施方式 Fig. 7 is a graph showing pulse discharge data of a battery assembly in which a primary battery and a secondary battery of the present invention are formed in parallel at a temperature of -40 ° C to 85 ° C in an embodiment of the present invention. detailed description

下面通过具体实施方式结合附图对本发明的实施方案或实施例作进一步详细说明，以便解释本发明的原理。下面足够详细地描述了这些实施方案或实施例，以使得所属领域技术人员能够实施本发明，然而应理解还可以利用其它实施方案，并且可以在不脱离本发明的精神的情况下作出改变。 The embodiments and examples of the present invention are further described in detail below with reference to the accompanying drawings, These embodiments or implementations are described in sufficient detail below For example, the invention may be practiced by those skilled in the art, but it is understood that other embodiments may be utilized and changes may be made without departing from the spirit of the invention.

在本发明中，术语 "宽温度范围" 是一个相对的概念，特别是指能够跨越现有技术的电池的使用温度的宽范围。例如，本发明的可充电二次锂离子电池可在 -40°C-85°C的宽度范围内使用，而本发明的一次电池则可在 -60°C-85°C的温度范围内使用。 In the present invention, the term "wide temperature range" is a relative concept, particularly referring to a wide range of operating temperatures that can span the prior art batteries. For example, the rechargeable secondary lithium ion battery of the present invention can be used in a width range of -40 ° C to 85 ° C, and the primary battery of the present invention can be used in a temperature range of -60 ° C to 85 ° C. .

根据本发明的可充电二次锂离子电池，其包括阴极材料、阳极材料、隔膜和电解液，其中，所述的阳极材料为阳极复合材料，且所述的可充电二次锂离子电池中的所述阴极材料可逆地结合锂离子的容量与所述阳极复合碳^材料以 LiC₆形式可逆地结合锂离子的容量之比在 0.5:1至 2:1之间。 A rechargeable secondary lithium ion battery according to the present invention, comprising a cathode material, an anode material, a separator, and an electrolyte, wherein the anode material is an anode composite material, and the rechargeable secondary lithium ion battery The ratio of the capacity of the cathode material to reversibly bind lithium ions to the capacity of the anode composite carbon material to reversibly bind lithium ions in the form of LiC ₆ is between 0.5:1 and 2:1.

具体地，所述的阳极复合材料包括复合碳^材料，该复合碳^材料包括基本碳^材料和微结构碳^材料，所述基本碳^材料选自石墨、焦炭、炭黑、硬碳、软碳及其组合，所述微结构碳 ^材料选自石墨烯、石墨烯微片、单层碳纳米管、多层碳纳米管、中间相微球碳、微孔活性碳及其组合。 Specifically, the anode composite material comprises a composite carbon material comprising a basic carbon material and a microstructure carbon material, wherein the basic carbon material is selected from the group consisting of graphite, coke, carbon black, hard carbon, The soft carbon and the combination thereof are selected from the group consisting of graphene, graphene microchips, single-walled carbon nanotubes, multi-walled carbon nanotubes, mesophase microsphere carbon, microporous activated carbon, and combinations thereof.

在一个实施例中，所述基本碳^材料的颗粒尺度在 0.5-100微米之间。较佳地，所述基本碳^材料的颗粒尺度在 0.8-50微米之间。所述微结构碳 ^材料相应的微结构尺度小于 2微米；优选地，所述微结构碳^材料相应的微结构尺度小于 500纳米。 In one embodiment, the basic carbon material has a particle size between 0.5 and 100 microns. Preferably, the basic carbon material has a particle size between 0.8 and 50 microns. The microstructural carbon material has a corresponding microstructure dimension of less than 2 microns; preferably, the microstructured carbon material has a corresponding microstructure dimension of less than 500 nanometers.

进一步，所述微结构碳 ^材料在所述复合碳 ^材料中的^量占比在 0.5%-50%之间，优选地，所述微结构碳 ^材料在所述复合碳 ^材料中的^量占比在 3-50%之间。 Further, the proportion of the microstructured carbon material in the composite carbon material is between 0.5% and 50%, and preferably, the microstructured carbon material is in the composite carbon material. ^ The proportion is between 3-50%.

在本发明的可充电二次锂离子电池中，所述可充电二次锂离子电池中阳极材料还包含粘合剂和导电剂，所述粘合剂和导电剂相对所述阳极材料的总^量占比小于 30%。较佳地，所述粘合剂和导电剂相对所述阳极材料的总^量占比小于 10% o In the rechargeable secondary lithium ion battery of the present invention, the anode material in the rechargeable secondary lithium ion battery further comprises a binder and a conductive agent, and the total amount of the binder and the conductive agent relative to the anode material The proportion is less than 30%. Preferably, the ratio of the binder and the conductive agent to the total amount of the anode material is less than 10% o

所述可充电二次锂离子电池中阴极材料包括锂化过渡金属插层材料，该锂化过渡金属插层材料选自锂化过渡金属氧化物、混合的锂化过渡金属盐和锂化金属磷酸盐的一种或多种。在一个实施例中，所述锂化过渡金属插层材料选自 The cathode material in the rechargeable secondary lithium ion battery comprises a lithiated transition metal intercalation material selected from the group consisting of lithiated transition metal oxides, mixed lithiated transition metal salts, and lithiated metal phosphates. One or more of the salts. In one embodiment, the lithiated transition metal intercalation material is selected from

LiCo0₂、 LiNi_xCo_1-x0₂、 LiNi_xAl_1-x0₂、 LiMn_xNi_yCo_z0₂、 LiNi_xCo_yAl_z0₂、 LiMn0₂、 LiFeP0₄及其组合，更优选 LiMn0₂、 LiNi_xCo_yAl_z0₂、 LiNi_xCo_1-x0₂、 LiMn_xNi_yCo_z0₂ 及其组合。而且，在所述锂化过渡金属插层材料中， Co在过渡金属元素中的摩尔比低于 25%。所述可充电二次锂离子电池包括隔膜，其与电解液与阳极材料和阴极材料接触并被电解液浸渍，其中，所述电解液包含至少一种相对低粘度的溶剂和至少一种具有相对高介电常数或具有低熔点及高沸点的溶剂，所述相对低粘度溶剂选自四氢呋喃、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、碳酸二丙酯、二乙二醇二甲醚、乙二醇二甲醚，所述具有相对高介电常数或具有低熔点及高沸点的溶剂选自碳酸乙酯、乙酸甲酯、丙酸甲酯、溴甲烷、甲酸甲酯、乙酸乙酯、丙酸乙酯、溴乙烷、碳酸丙烯酯、碳酸丁二醇酯、乙腈、二甲基亚砜、二甲基甲酰胺、 N-甲基吡咯烷酮及其混合物。进一步，所述电解液中至少含有一种具有在循环过程中保护电极表面的添加剂，所述添加剂选自碳酸亚乙烯酯、己烯雌酚、丁磺酸内酯、二甲疏醚中的一种或多种。此外，所述电解液中至少含有一种锂金属盐，所述锂金属盐选自 LiPF₆、 LiBF₄、 LiBOB、 LiTFSI、 LiC10₄及其组合。在一个实施例中，所述电解液包括碳酸乙酯：碳酸二甲酯：碳酸甲乙酯：碳酸二乙酯：乙酸丙酯的混合溶剂体系，并包含溶解于其中的锂金属盐以及添加剂。进一步所述混合溶剂体系中各溶剂在总混合溶剂体系中的摩尔比范围为碳酸乙酯： 5%~55%、碳酸甲乙酯： 1%〜55%、碳酸二乙酯： 3%〜 50%、碳酸二甲酯： 5%〜70%、乙酸丙酯： 5%〜60%。较佳地，所述添加剂相对所述混合溶剂体系的摩尔比范围为 5%〜75%，例如为 5%、 15%、 30%、 50% 或 75%。 LiCo0 ₂ , LiNi _x Co _1-x 0 ₂ , LiNi _x Al _1-x 0 ₂ , LiMn _x Ni _y Co _z 0 ₂ , LiNi _x Co _y Al _z 0 ₂ , LiMn0 ₂ , LiFeP0 ₄ and combinations thereof, more preferably LiMn0 ₂ , LiNi _x Co _y Al _z 0 ₂ , LiNi _x Co _1-x 0 ₂ , LiMn _x Ni _y Co _z 0 ₂ and combinations thereof. Moreover, in the lithiated transition metal intercalation material, the molar ratio of Co in the transition metal element is less than 25%. The rechargeable secondary lithium ion battery includes a separator in contact with an anode material and a cathode material and impregnated with an electrolyte, wherein the electrolyte contains at least one relatively low viscosity solvent and at least one has a relative a high dielectric constant or a solvent having a low melting point and a high boiling point, the relatively low viscosity solvent being selected from the group consisting of tetrahydrofuran, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, dipropyl carbonate, and Ethylene glycol dimethyl ether, ethylene glycol dimethyl ether, the solvent having a relatively high dielectric constant or having a low melting point and a high boiling point is selected from the group consisting of ethyl carbonate, methyl acetate, methyl propionate, methyl bromide, formic acid Ester, ethyl acetate, ethyl propionate, ethyl bromide, propylene carbonate, butylene glycol carbonate, acetonitrile, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone and mixtures thereof. Further, the electrolyte contains at least one additive having a surface for protecting the electrode during the cycle, and the additive is selected from one or more of vinylene carbonate, diethylstilbestrol, butane sultone, and dimethyl ketone. Kind. Further, the electrolyte contains at least one lithium metal salt selected from the group consisting of LiPF ₆ , LiBF ₄ , LiBOB, LiTFSI, LiC10 ₄ and combinations thereof. In one embodiment, the electrolyte comprises ethyl carbonate: dimethyl carbonate: ethyl methyl carbonate: diethyl carbonate: a mixed solvent system of propyl acetate, and contains a lithium metal salt dissolved therein and an additive. Further, the molar ratio of each solvent in the mixed solvent system in the mixed solvent system is ethyl carbonate: 5% to 55%, ethyl methyl carbonate: 1% to 55%, and diethyl carbonate: 3% to 50. %, dimethyl carbonate: 5% to 70%, propyl acetate: 5% to 60%. Preferably, the molar ratio of the additive to the mixed solvent system ranges from 5% to 75%, for example, 5%, 15%, 30%, 50% or 75%.

本发明的可充电二次锂离子电池能在宽温度范围内工作，即所述的电池可在较的宽温度范围完成充电和放电动作。例如，本发明的可充电二次锂离子电池可以在 -40°C-85°C的温度范围内实现充电和放电功能。相对于现有技术，本发明的可充电二次锂离子电池大大改善了现有技术中的可充电二次锂离子电池在低温环境下不能正常工作的问题，实现极限低温和极限高温的正常充电和放电。 The rechargeable secondary lithium ion battery of the present invention can operate over a wide temperature range, i.e., the battery can perform charging and discharging operations over a relatively wide temperature range. For example, the rechargeable secondary lithium ion battery of the present invention can perform charging and discharging functions in a temperature range of -40 ° C to 85 ° C. Compared with the prior art, the rechargeable secondary lithium ion battery of the invention greatly improves the problem that the rechargeable secondary lithium ion battery in the prior art cannot work normally in a low temperature environment, and realizes the normal charging of the extreme low temperature and the extreme high temperature. And discharge.

以下结合附图说明本发明的一次电池和二次电池并联而成的电池组的结构和性能。 The structure and performance of the battery pack in which the primary battery and the secondary battery of the present invention are connected in parallel will be described below with reference to the drawings.

首先参照图 2，该图是根据本发明的一个实施方案的锂电池组件的电路设计，包括一次锂 /)¾氧化物电池 2以及可充电二次锂离子电池 7，其中一次电池 2 与二次电池 7通过导电连接进行并联。当接入端 8、 9间接入负载而需要电路 6 提供大电流时，部分电流可由二次电池 7输出从而降低对一次电池 2的电流需求。该锂电池组件的典型特点在于，可充电二次锂离子电池 7 充满状态下的开路电压高于并联的一次锂 /(¾氧化物电池 2的开路电压，从而使两者并联且负载端开路条件下可充电二次锂离子电池 7 的电压低于充满状态的电压，以减轻老化以及副反应导致的自放电现象。所谓"可充电二次锂离子电池 7充满状态下的开路电压高于并联的一次锂 /(¾氧化物电池 2的开路电压"，是指略高即可，例如以一次锂 / 1¾氧化物电池的开路电压为计算基础，可充电二次锂离子电池充满状态下的开路电压可以比一次锂 /(¾氧化物电池的开路电压高出例如 10%以下，优选高出 5%以下，更优选高出 2%以下，最优选高出 1%以下。若以高出一次锂 / 卤氧化物电池的开路电压的绝对量计算，可充电二次锂离子电池充满状态下的开路电压可以比一次锂 /(¾氧化物电池的开路电压高出例如 0.3V以下，优选高出 0.1V以下，更优选高出 0.05V以下，最优选高出 0.02V以下，例如高出 0.01V。 Referring first to Figure 2, there is shown a circuit design of a lithium battery pack according to an embodiment of the present invention, comprising a primary lithium/) 3⁄4 oxide battery 2 and a rechargeable secondary lithium ion battery 7, wherein the primary battery 2 and the secondary The batteries 7 are connected in parallel by means of an electrically conductive connection. When the access terminals 8, 9 are connected to the load and the circuit 6 is required to supply a large current, part of the current can be output from the secondary battery 7 to lower the current demand on the primary battery 2. A typical feature of the lithium battery pack is that the open circuit voltage in the fully charged state of the rechargeable secondary lithium ion battery 7 is higher than the open circuit voltage of the parallel lithium/(3⁄4 oxide battery 2), so that the two are connected in parallel and the load end is open. The voltage of the secondary rechargeable lithium-ion battery 7 is lower than the voltage of the full state to relieve the old And the self-discharge phenomenon caused by side reactions. The so-called "rechargeable secondary lithium-ion battery 7 open circuit voltage in the full state is higher than the parallel lithium / (3⁄4 oxide battery 2 open circuit voltage), which means slightly higher, such as a primary lithium / 13⁄4 oxide battery The open circuit voltage is the basis of calculation, and the open circuit voltage in the full state of the rechargeable secondary lithium ion battery may be, for example, 10% or less, preferably 5% or less, more preferably higher than the open circuit voltage of the primary lithium/(3⁄4 oxide battery). 2% or less, most preferably 1% or less. If the absolute value of the open circuit voltage of the lithium/halide oxide battery is higher than that of the secondary lithium-halide oxide battery, the open circuit voltage of the rechargeable secondary lithium ion battery can be higher than that of the primary lithium/ (The open circuit voltage of the 3⁄4 oxide battery is, for example, 0.3 V or less, preferably 0.1 V or more, more preferably 0.05 V or less, and most preferably 0.02 V or more, for example, 0.01 V higher.

需要说明的是，图 2示出的是只有一个一次锂 /(¾氧化物电池的实施方案。在其它实施方案中，为满足不同应用要求，需要提升电池组件容量的情况下，可以采用多个一次锂 / (¾氧化物电池并联的方式。 It should be noted that FIG. 2 shows an embodiment of only one primary lithium/(3⁄4 oxide battery). In other embodiments, in order to meet different application requirements and need to increase the capacity of the battery assembly, multiple Primary lithium / (3⁄4 oxide battery in parallel).

发明人在图 2 所示的实施方案的基础上，进一步研究发现调整阴极材料可逆地结合锂离子的容量与阳极材料可逆地结合锂离子的容量之比，对于进一步改善可充电二次锂离子电池的性能，从而提高上述锂电池组件的整体性能有帮助。具体的，可充电二次锂离子电池中包含阴极材料和阳极复合碳^材料，其中阴极材料可逆地结合锂离子的容量与阳极复合碳^材料以 LiC₆形式可逆地结合锂离子的容量之比在 0.5:1至 2:1之间，这样降低了充电过程中锂离子***碳材料时锂金属在其表面的沉积形成枝晶以及发生副反应的风险。 On the basis of the embodiment shown in FIG. 2, the inventors further found that adjusting the ratio of the capacity of the cathode material to reversibly bind lithium ions to the capacity of the anode material to reversibly combine lithium ions, for further improving the rechargeable secondary lithium ion battery The performance, which improves the overall performance of the above lithium battery components, is helpful. Specifically, the rechargeable secondary lithium ion battery comprises a cathode material and an anode composite carbon material, wherein the ratio of the capacity of the cathode material reversibly combining the lithium ions to the capacity of the anode composite carbon material to reversibly combine the lithium ions in the form of LiC ₆ Between 0.5:1 and 2:1, this reduces the risk of lithium metal depositing on the surface of the lithium metal during the charging process to form dendrites and side reactions.

本发明的一个实施例中，所述一次锂 /(¾氧化物电池通常（但非限定性地）可以是锂 /亚疏酰氯电池或锂 /疏酰氯电池；尤其是工作电压为 3.67V的锂 /亚疏酰氯电池或工作电压为 3.9V的锂 /疏酰氯电池。 In one embodiment of the invention, the primary lithium/(3⁄4 oxide battery) can be, but is not limited to, a lithium/thionoyl chloride battery or a lithium/thionochloride battery; especially lithium with an operating voltage of 3.67V. / Sub-acid chloride battery or lithium / acyl chloride battery operating at 3.9V.

现参照图 3，该图是本发明的一个实施方案的锂电池组件中，可充电二次锂离子电池的电极叠成部分的示意性截面视图。 Referring to Fig. 3, which is a schematic cross-sectional view showing an electrode stack portion of a rechargeable secondary lithium ion battery in a lithium battery module according to an embodiment of the present invention.

图 3示例说明可用于图 2中的二次电池 7部分。其中可充电二次锂离子电池部分包括阳极 15、阴极 16以及隔膜 12。其中阳极 15可包括阳极导电支撑件 11，可选自导电聚合物、碳、铝、铜、镍、不锈钢、铬、金及其组合的材料。阳极导电支撑件 11的厚度优选 5-100微米，更优选 10-20微米，但不限其它厚度数值。阳极导电支撑件 11上涂覆并优选两面涂覆主要由复合碳^材料组成的阳极活性材料 10。阳极活性材料 10除复合碳^材料之外也可以包含粘合剂以及导电剂，但粘合剂和导电剂相对阳极材料的总^量占比小于 30%，，例如粘合剂和导电剂相对阳极材料的总^量占比可以是 25%、 20%、 15%、 10%、 5%或 2%。较佳的是小于或等于 20%，例如 15%或 10%。粘合剂和导电剂是非电池活性材料，在电极材料中起辅助性（成膜及辅助导电）作用。过高的粘合剂和导电剂 ^量占比会导致有效活性材料相对减少，影响电池容量。本发明的粘合剂和导电剂在上述^量占比的情况下，既能充分发挥辅助性作用，又不会影响影响电池容量。其中复合碳^材料由至少两种材料组成，包括基本碳^材料以及微结构碳^材料。所述基本碳^材料是传统锂离子电池的主要活性阳极物^，其优点在于相对较高的锂离子嵌入比容量（即容量密度）以及相对较低的材料成本。微结构碳^材料在锂离子电池电极材料中也有应用，其具体工作机制在不同条件下不同。在本发明中，提供非嵌入式储锂机制，从而提升充放电过程的倍率能力。本发明中采用包含上述两种材料的复合碳^材料，能够在所需要大电流放电性能以及容量方面取得发明所针对应用需要的平衡性能。所述基本碳^材料通常但非限定性地可以选自石墨、焦炭、炭黑、硬碳、软碳及其组合，所述微结构碳^材料通常但非限定性地可以选自石墨烯（Graphene)、石墨烯微片 (Graphene nanoplatelet) ,单层碳纳米管（SWCNT)、多层碳纳米管（MWCNT)、中间相微球碳（MCMB)、微孔活性碳及其组合。其中基本碳^材料的颗粒尺度在 0.5-100微米之间，例如可以是 0.5微米、 0.8微米、 10微米、 50微米或 80 微米。较佳的是 0.8-80微米之间，例如为 1微米、 5微米、 20微米或 50微米。更佳的是 0.8-50微米之间，例如是 1微米或 10微米等。在上述范围内的颗粒可在压实密度、成膜性能以及锂离子扩散深度方面取得较好的平衡。所述微结构碳^材料相应的微结构尺度（例如厚度、直径或空隙等）小于 2微米，优选小于 500 纳米，微结构尺度越低，比表面积越大，储锂能力以及快速放电能力越好。微结构碳^材料在复合碳 ^材料中的^量占比在 0.5%-50%之间能取得优异的效果，因为微结构碳 ^材料低于基本碳^材料，不会使电池比容量有太明显的降低。通常微结构碳^材料在复合碳^材料中的^量占比可以是 0.5%-50%之间，或者在 3%-50%之间。 FIG. 3 illustrates a portion of the secondary battery 7 that can be used in FIG. 2. The rechargeable secondary lithium ion battery portion includes an anode 15, a cathode 16, and a separator 12. The anode 15 can include an anode conductive support 11 that can be selected from the group consisting of conductive polymers, carbon, aluminum, copper, nickel, stainless steel, chromium, gold, and combinations thereof. The thickness of the anode conductive support 11 is preferably 5 to 100 μm, more preferably 10 to 20 μm, but is not limited to other thickness values. The anode active support member 11 is coated and preferably coated on both sides with an anode active material 10 mainly composed of a composite carbon material. The anode active material 10 may further comprise a binder and a conductive agent in addition to the composite carbon material, but the ratio of the binder and the conductive agent to the anode material is less than 30%, for example, the binder and the conductive agent are relatively The total amount of anode material may be 25%, 20%, 15%, 10%, 5% or 2%. It is preferably less than or equal to 20%, such as 15% or 10%. The binder and the conductive agent are non-battery active materials that function as an auxiliary (film formation and auxiliary conduction) in the electrode material. Excessive adhesive and conductive agent ^ The ratio of the amount will lead to a relative decrease in the effective active material, affecting the battery capacity. In the case where the binder and the conductive agent of the present invention have a ratio of the above-mentioned amount, the auxiliary effect can be sufficiently exerted without affecting the battery capacity. The composite carbon material is composed of at least two materials, including a basic carbon material and a microstructure carbon material. The basic carbon material is the main active anode of a conventional lithium ion battery, which has the advantages of relatively high lithium ion intercalation specific capacity (i.e., capacity density) and relatively low material cost. Microstructured carbon materials are also used in lithium ion battery electrode materials, and their specific working mechanisms are different under different conditions. In the present invention, a non-embedded lithium storage mechanism is provided to enhance the rate capability of the charge and discharge process. In the present invention, a composite carbon material comprising the above two materials is used, and the balance performance required for the application of the invention can be obtained in terms of the required large current discharge performance and capacity. The basic carbon material may be generally, but not limited to, selected from the group consisting of graphite, coke, carbon black, hard carbon, soft carbon, and combinations thereof, and the microstructured carbon material may be generally, but not limited to, selected from graphene ( Graphene), Graphene nanoplatelet, single-walled carbon nanotube (SWCNT), multi-walled carbon nanotube (MWCNT), mesophase microsphere carbon (MCMB), microporous activated carbon, and combinations thereof. Wherein the basic carbon material has a particle size between 0.5 and 100 microns, for example 0.5 microns, 0.8 microns, 10 microns, 50 microns or 80 microns. It is preferably between 0.8 and 80 microns, for example 1 micron, 5 micron, 20 micron or 50 micron. More preferably, it is between 0.8 and 50 microns, such as 1 or 10 microns. Particles within the above range can achieve a good balance between compaction density, film forming properties, and lithium ion diffusion depth. The microstructural carbon material has a corresponding microstructure dimension (such as thickness, diameter or void, etc.) of less than 2 micrometers, preferably less than 500 nanometers, and the lower the microstructure scale, the larger the specific surface area, the better the lithium storage capacity and the rapid discharge capability. . The microstructure of the carbon material in the composite carbon material can have an excellent effect in the range of 0.5% to 50%, because the microstructure carbon material is lower than the basic carbon material, and the specific capacity of the battery is not Too obvious reduction. Generally, the proportion of the microstructured carbon material in the composite carbon material may be between 0.5% and 50%, or between 3% and 50%.

阴极 16包括阴极导电支撑件 14，可选自导电聚合物、碳、铝、铜、镍、不锈钢、铬、金及其组合的材料。阴极导电支撑件 14的厚度优选 5-100微米，更优选 10-20微米，但不限其它厚度数值。阴极导电支撑件 14上涂覆并优选两面涂覆主要由锂化过渡金属插层材料组成的阴极活性材料 13。其中锂化过渡金属插层材料通常但非限定性地可以选自锂化过渡金属氧化物、混合的锂化过渡金属盐和锂化金属磷酸盐的一种或多种，优选 LiCo0₂、 LiNi_xCo_1-x0₂, LiNi_xAl_1-x0₂, LiMn_xNi_yCo_z0₂、 LiNi_xCo_yAl_z0₂、 LiMn0₂、 LiFeP0₄及其组合，更优选 LiMn0₂、 LiNi_xCo_yAl_z0₂、 LiNi_xCoi_-x0₂, LiMn_xNi_yCo_z0₂及其组合。这些化学式表示的物^ 具有本领域的一般性概念，其中各化学式中的 _x、 y和 z等具有本领域的一般性数值，这些数值是本领域公知的内容。虽然如此，在本发明的一些优选实施例中， Mn的角标取值在 0.3~0.9， Ni的角标取值在 0.3~0.9， A1在独立角标情况下 (非关联取值）取值在 0.05~0.3， Co的角标取值限定在 0.05~0.25之间。应当理解，这里所给出的取值范围仅是示例性的，不应当理解为对本领域中一般性取值的限制。 Cathode 16 includes a cathode conductive support 14, which may be selected from the group consisting of conductive polymers, carbon, aluminum, copper, nickel, stainless steel, chromium, gold, and combinations thereof. The thickness of the cathode conductive support 14 is preferably from 5 to 100 micrometers, more preferably from 10 to 20 micrometers, but is not limited to other thickness values. The cathode active support member 14 is coated and preferably coated on both sides with a cathode active material 13 consisting essentially of a lithiated transition metal intercalation material. Wherein the lithiated transition metal intercalation material may be generally, but not limited to, selected from one or more of a lithiated transition metal oxide, a mixed lithiated transition metal salt, and a lithiated metal phosphate, preferably LiCo0 ₂ , LiNi _x Co _1-x 0 ₂ , LiNi _x Al _1-x 0 ₂ , LiMn _x Ni _y Co _z 0 ₂ , LiNi _x Co _y Al _z 0 ₂ , LiMn0 ₂ , LiFeP0 ₄ and combinations thereof, more preferably LiMn0 ₂ , LiNi _x Co _y Al _z 0 ₂ , LiNi _x Coi - _x 0 ₂ , LiMn _x Ni _y Co _z 0 ₂ and combinations thereof. The formulas represented by these formulas have the general concept in the art, wherein _x , y and z in each chemical formula have general values in the art, and these values are well known in the art. Nonetheless, some preferred embodiments of the invention In the middle, the angle of Mn is 0.3~0.9, the value of Ni is 0.3~0.9, and the value of A1 is 0.05~0.3 in the case of independent angular standard. The value of Co is the value of Co. Limited to between 0.05 and 0.25. It should be understood that the range of values given herein is merely exemplary and should not be construed as limiting the general value in the art.

在一个实施例中，锂化过渡金属插层材料中， Co在过渡金属元素中的摩尔比低于 25%，例如是 20%、 15%、 10%或 5%等。 In one embodiment, in the lithiated transition metal intercalation material, the molar ratio of Co in the transition metal element is less than 25%, for example, 20%, 15%, 10% or 5%.

隔膜 12是用于将阴极与阳极隔开的隔膜材料，并且电解液可以浸渍该隔膜。这样的隔膜材料可以为任意合适的多孔非导电材料，例如但不限于具有微孔结构的聚丙烯膜、或任何其他合适的隔膜材料。 The separator 12 is a separator material for separating the cathode from the anode, and the electrolyte may impregnate the separator. Such a membrane material can be any suitable porous non-conductive material such as, but not limited to, a polypropylene film having a microporous structure, or any other suitable membrane material.

可充电二次锂离子电池中包含与阳极材料和阴极材料接触并浸渍隔膜的电解液，该电解液包含至少一种相对低粘度溶剂和至少一种具有相对高介电常数或具有低熔点及高沸点的溶剂，其中低粘度溶剂保证在不同条件下的离子输运性能；高介电常数溶剂保证低的漏电率；低熔点及高沸点溶剂保证电池在高低温使用条件下的稳定性。相对低粘度溶剂通常但非限定性地可以选自四氢呋喃 The rechargeable secondary lithium ion battery includes an electrolyte contacting the anode material and the cathode material and impregnating the separator, the electrolyte comprising at least one relatively low viscosity solvent and at least one having a relatively high dielectric constant or having a low melting point and a high The boiling point solvent, wherein the low viscosity solvent guarantees the ion transport performance under different conditions; the high dielectric constant solvent guarantees the low leakage rate; the low melting point and high boiling point solvent ensure the stability of the battery under high and low temperature use conditions. The relatively low viscosity solvent can be selected from tetrahydrofuran, usually but not limitedly.

( tetrahydrofuran/THF ) , 碳酸二甲酯（dimethyl carbonate/DMC ) , 碳酸二乙酯(tetrahydrofuran/THF) , dimethyl carbonate/DMC , diethyl carbonate

( diethyl carbonate/DEC ) , 碳酸甲乙酯（ ethyl methyl carbonate/EMC ) , 碳酸甲丙酉旨 (methyl propyl carbonate/MC) ^ 碳酸二丙酉旨 (dipropyl carbonate) ^ 二乙二醇二甲醚（diglyme；)、乙二醇二甲醚（1,2 dimethoxyethane) 及其组合；具有相对高介电常数或具有低熔点及高沸点的溶剂通常但非限定性地可以选自碳酸乙酯(diethyl carbonate/DEC) , ethyl methyl carbonate (EMC ) , methyl propyl carbonate / MC ^ dipropyl carbonate ^ diethylene glycol dimethyl ether ( Diglyme;), 1,2 dimethoxyethane, and combinations thereof; a solvent having a relatively high dielectric constant or having a low melting point and a high boiling point, usually but not limitedly, may be selected from ethyl carbonate

( ethylene carbonate/EC )、乙酸甲酉旨 ( methyl acetate )、丙酸甲酉旨 ( methyl propanoate/MP) , 溴甲燒 ( methyl bromide/MB ) , 甲酉甲酯 (methyl formate/MF) , 乙酸乙酯（ethyl acetate/EA) , 乙酸丙酯（propyl acetate/PA) , 丙酸乙酯（ethyl propanoate/EP) ^ 漠乙燒 (ethyl bromide )、碳酸丙婦酉旨 (propylene carbonate)、碳酸丁二醇酯（butylene carbonate)、乙腈（acetonitrile)、二甲基亚砜 (dimethyl sulfoxide ) , 二甲基甲酰胺（ Dimethylformamide ) , Ν-甲基吡咯烷酮(ethylene carbonate/EC), methyl acetate, methyl propanoate/MP, methyl bromide/MB, methyl formate/MF, acetic acid Ethyl acetate (EA), propyl acetate/PA, ethyl propanoate/EP ^ethyl bromide, propylene carbonate, butyl carbonate Butyl carbonate, acetonitrile, dimethyl sulfoxide, dimethylformamide, Ν-methylpyrrolidone

( N-methyl-pyrrolidone/NMP ) 及其组合。此外，上述可充电二次锂离子电池电解液中，至少含有一种具有在循环过程中保护电极表面的添加剂，该添加剂通常但非限定性地可以选自碳酸亚乙烯酯（ vinylene carbonate )、己烯雌酚(N-methyl-pyrrolidone/NMP) and combinations thereof. Further, the above-mentioned rechargeable secondary lithium ion battery electrolyte contains at least one additive having a surface for protecting the electrode during the cycle, and the additive may be generally, but not limited to, selected from vinylene carbonate and diethylstilbestrol.

(diethylstilbestrol) , 丁橫酸内酯 (Butanesultone) , 二甲疏醚 (dimethyl sulfide) 中的一种或多种。此外，上述可充电二次锂离子电池电解液中，至少含有一种锂金属盐，该锂金属盐通常但非限定性地可以选自 LiPF₆、LiBF₄、LiBOB、LiTFSI、 LiC10₄及其组合 (diethylstilbestrol), one or more of Butanesultone, dimethyl sulfide. Further, the rechargeable secondary lithium ion battery electrolyte contains at least one lithium metal salt, and the lithium metal salt may be generally, but not limited to, selected from the group consisting of LiPF ₆ , LiBF ₄ , LiBOB, LiTFSI, LiC 10 _{4 ,} and combinations thereof.

在本发明的一个实施例中，可充电二次锂离子电池电解液组合包括 EC:DMC:EMC:DEC:PA 的混合溶剂体系，并包含溶解于其中的锂金属盐以及添加剂。较佳地，所述混合溶剂体系中各溶剂在总混合溶剂体系中的摩尔比范围为 EC: 5%~55%、 EMC: 1%〜55%、 DEC: 3%〜50%、 DMC: 5%〜70%、 PA: 5%〜60%；优选地，添加剂相对混合溶剂体系的摩尔比范围为 5%〜75%。这样的体系具有平衡锂盐的溶解性、离子导电率以及高低温工作状态下的稳定性的作用。 In one embodiment of the invention, the rechargeable secondary lithium ion battery electrolyte combination includes EC: DMC: EMC: DEC: A mixed solvent system of PA, and contains lithium metal salts and additives dissolved therein. Preferably, the molar ratio of each solvent in the mixed solvent system in the total mixed solvent system is EC: 5% to 55%, EMC: 1% to 55%, DEC: 3% to 50%, DMC: 5 %~70%, PA: 5%~60%; Preferably, the molar ratio of the additive to the mixed solvent system ranges from 5% to 75%. Such a system has the effect of balancing the solubility of the lithium salt, the ionic conductivity, and the stability under high and low temperature operating conditions.

以下通过具体实施例详细说明本发明的实施方案及其有益效果，应当理解这些实施例并不构成对本发明保护范围的限制，本发明的保护范围以权利要求为依据。 The embodiments of the present invention and the beneficial effects thereof are described in detail below by way of specific examples, which are not to be construed as limiting the scope of the invention.

实施例 1 Example 1

为演示本发明的实施方案的优越性能，根据本发明所涉及的方案构建了一个可充电二次锂离子电池，并进行了相关的基本测试。 To demonstrate the superior performance of embodiments of the present invention, a rechargeable secondary lithium ion battery was constructed in accordance with the teachings of the present invention and related basic tests were performed.

使用下列元件制造软包型试验电池。阳极选用 9 微米铜箔，在铜箔的两侧涂布厚度为 27.5微米（每侧）的碳基阳极：碳粉： PVDF (80:10: 10w%) 的硬^ 材料混合物层。碳基阳极材料颗粒为片状，厚度为 100-200 纳米，直径为 500 纳米至 5微米，阳极总厚度是 64微米，阳极的宽度是 22毫米，并且阳极长度是 1185毫米。在本文中， "w% " 都表示^量百分比。 A soft pack type test cell was fabricated using the following components. The anode is made of 9 micron copper foil and coated on both sides of the copper foil with a thickness of 27.5 micrometers (each side) of carbon-based anode: carbon powder: PVDF (80:10: 10w%) layer of hard material mixture. The carbon-based anode material particles are in the form of flakes having a thickness of 100-200 nm, a diameter of 500 nm to 5 μm, a total anode thickness of 64 μm, an anode width of 22 mm, and an anode length of 1185 mm. In this article, "w%" means the percentage of the amount.

阴极选用 20微米铝箔作为载体，在铝箔两侧分别涂布厚度为 24微米的阴极材料，该材料由 LiAlNiCo02、碳粉和 PVDF (按重量计分别为 80%、 10%和 10%) 的混合物制成。阴极的总厚度为 68微米，宽度为 18毫米，长度为 1125 毫米。阳极和阴极混合物中碳粉用来提高导电率，而 PVDF则用作粘合剂。 The cathode is made of 20 micron aluminum foil as a carrier, and a cathode material having a thickness of 24 micrometers is coated on both sides of the aluminum foil, and the material is made of a mixture of LiAlNiCo02, carbon powder and PVDF (80%, 10% and 10% by weight, respectively). to make. The cathode has a total thickness of 68 microns, a width of 18 mm, and a length of 1125 mm. Carbon powder in the anode and cathode mixture is used to increase conductivity, while PVDF is used as a binder.

电池采用 25微米厚 Celgard型薄膜分隔阴极和阳极，该薄膜为 PP-PE-PP三层复合膜。电解液采用 EC: EMC: DEC : DMC: PA ( 17.88 : 0.49: 19.96 : 17.15 : 44.53w%) 混合物，锂盐采用 LiPF6，其浓度为 1摩尔 /升。电池的叠层（包括阳极、阴极和加入它们之间的隔膜）如本领域已知的那样按照螺旋缠绕构型装配，之后放入铝塑膜中，烘干后在干燥环境中注液，随后真空封装及活化。该电池在 2.75-3.67V的电压范围内，采用 1C电流充放电，测得其容量约为 45mAh。实施例 2 The battery was separated by a 25 μm thick Celgard film, which was a PP-PE-PP three-layer composite film. The electrolyte was made of EC: EMC: DEC: DMC: PA ( 17.88 : 0.49: 19.96 : 17.15 : 44.53w%). The lithium salt was LiPF6 at a concentration of 1 mol / liter. The stack of cells (including the anode, the cathode, and the separator between them) are assembled in a spiral wound configuration as is known in the art, then placed in an aluminum plastic film, dried and then infused in a dry environment, followed by Vacuum encapsulation and activation. The battery is charged and discharged with a 1C current in the voltage range of 2.75-3.67V, and its capacity is about 45mAh. Example 2

如上述实施例 1 所述的流程和材料制造锂离子电池，其中，阳极材料使用的是球形碳基阳极材料，该球形碳基阳极材料的颗粒大小为 1微米至 10微米。该实施例中制得的电池在 2.75-3.76的电压范围内，采用 1C电流充放电，测得其容量约为 35mAh。实施例 3 A lithium ion battery is fabricated as in the flow and materials described in Example 1 above, wherein the anode material is a spherical carbon-based anode material having a particle size of from 1 micrometer to 10 micrometers. The battery produced in this example was charged and discharged with a current of 1 C in a voltage range of 2.75 to 3.76, and its capacity was measured to be about 35 mAh. Example 3

如上述实施例 1 所述的流程和材料制造锂离子电池，其中，阳极材料使用的是片状碳基材料，所述片状碳基材料的颗粒厚度为 500纳米至 21微米，直径大小为 30微米至 100微米。该电池在 2.75-3.76的电压范围内，采用 1C电流充放电，测得其容量约为 47mAh。 A lithium ion battery is fabricated according to the flow and materials described in Embodiment 1 above, wherein the anode material is a sheet-like carbon-based material having a particle thickness of 500 nm to 21 μm and a diameter of 30 Micron to 100 microns. The battery is charged and discharged with a 1C current in the voltage range of 2.75-3.76, and its capacity is about 47mAh.

实施例 4 Example 4

如上述实施例 1 所述的流程和材料制造锂离子电池，其中，阳极材料使用的是球形碳基材料，球所述形碳基材料直径大小为 5微米至 20微米。该电池在 2.75-3.76的电压范围内，采用 1C电流充放电，测得其容量约为 43mAh。 The lithium ion battery is fabricated by the flow and materials described in the above embodiment 1, wherein the anode material is a spherical carbon-based material, and the spherical carbon-based material has a diameter of 5 μm to 20 μm. The battery is charged and discharged with a 1C current in the voltage range of 2.75-3.76, and its capacity is about 43mAh.

实施例 5 Example 5

如上述实施例 1 所述的流程和材料制造锂离子电池，其中，微结构碳^材料： PVDF: 碳基阳极材料的比例为 0.5 : 1 : 98.5。该电池在 2.75-3.76的电压范围内，采用 1C电流充放电，测得其容量约为 53mAh。 A lithium ion battery is fabricated according to the flow and materials described in Embodiment 1 above, wherein the microstructure of the carbon material: PVDF: the ratio of the carbon-based anode material is 0.5:1:98.5. The battery is charged and discharged with a 1C current in the voltage range of 2.75-3.76, and its capacity is about 53mAh.

实施例 6 Example 6

如上述实施例 1 所述的流程和材料制造锂离子电池，其中，微结构碳^材料： PVDF: 碳基阳极材料的比例为 50: 10: 40。其中微结构碳^材料为 Super-P 和活性炭的混合物，该电池在 2.75-3.76的电压范围内，采用 1C电流充放电，测得其容量约为 18 mAh。 A lithium ion battery is fabricated according to the flow and materials described in Embodiment 1 above, wherein the ratio of the microstructured carbon material: PVDF: carbon-based anode material is 50:10:40. The microstructure carbon material is a mixture of Super-P and activated carbon. The battery is charged and discharged with a 1C current in the voltage range of 2.75-3.76, and its capacity is about 18 mAh.

图 4 演示了本发明的一个实施例中的电池的充放电特性。其中示出了可充电二次锂离子电池在充满状态下的电压约为 3.68V,容量值约 43毫安时（mAh)。其开路电压在充满状态下开路电压略高于常用的一次锂 /亚疏酰氯（Li/SOC12) 电池（3.67V) 的开路电压，因此在并联状态下一方面可以尽量利用二次电池的容量，同时也减轻过度充满状态下的漏电现象。 Figure 4 illustrates the charge and discharge characteristics of a battery in one embodiment of the present invention. It shows that the chargeable secondary lithium ion battery has a voltage of about 3.68 V in a full state and a capacity value of about 43 mAh (mAh). The open circuit voltage of the open circuit voltage is slightly higher than the open circuit voltage of the commonly used primary lithium/sub-acid chloride (Li/SOC12) battery (3.67V), so the capacity of the secondary battery can be utilized as much as possible in the parallel state. At the same time, it also reduces the leakage phenomenon in the overfilled state.

图 5 展示了本发明的一个实施例中所构建可充电二次锂离子电池在低温大电流条件下的瞬态放电特性。在一个实施例中，放电条件为充满状态下，在 -40°C 环境中以 7C倍率（300mA) 放电。其中使用同样容量的一般商业电池在同等条件下进行实验作为比较。在图 5 中可见，依据本发明方案制作的电池在低温条件下以 300mA大电流进行放电， 2秒钟之内输出电压仍可維持在约 2.8V, 高于常见通讯电子器件所需最低电压（如 2.5V)。然而作为比较的商业锂离子电池，在少于 0.5秒的放电时间内，电压急剧下降至 1.5V及以下，失去继续向相关设备供电的能力。 Figure 5 is a graph showing the transient discharge characteristics of a rechargeable secondary lithium ion battery constructed in one embodiment of the present invention under low temperature and high current conditions. In one embodiment, the discharge condition is a full state, and discharge is performed at a rate of 7 C (300 mA) in an -40 ° C environment. A general commercial battery of the same capacity was used for experiments under the same conditions as a comparison. As can be seen in FIG. 5, the battery fabricated according to the inventive scheme discharges at a high current of 300 mA under low temperature conditions, and the output voltage can be maintained at about 2.8 V in 2 seconds, which is higher than the minimum voltage required for common communication electronic devices ( Such as 2.5V). However, as a comparative commercial lithium-ion battery, the voltage drops sharply to 1.5V and below during a discharge time of less than 0.5 seconds, losing the ability to continue to supply power to the relevant equipment.

图 6 所示为在本发明的一个实施例中，本发明的可充电二次锂离子电池在 -40°C、 -25°C、 20°C和 85°C的温度下，在 10秒时间内，放电电流为 350mA的电压随时间的变化曲线。由图可知，在极限的低温条件下（-40°C )，本发明的可充电二次锂离子电池依然具有较好的放电性能，在接近 9C的大电流放电情况下保持电压在 2V以上，能满足大部分电子设备在低温情况下的使用，且可以在该温度（-40°C ) 下重新进行充电。随着实验温度的升高，本发明的可充电二次锂离子电池在整个测试的 10秒的放电时间内的放电情况都維持在较高的工作电压，特别是在高温下（85°C ) 能保持与常温下几乎相同的放电性能，且也同样可以可以在该温度（85°C ) 下重新进行充电。 Figure 6 shows a rechargeable secondary lithium ion battery of the present invention in one embodiment of the present invention. -40 ° C, -25 ° C, 20 ° C and 85 ° C temperature, within 10 seconds, the discharge current is 350 mA voltage versus time curve. It can be seen from the figure that the rechargeable secondary lithium ion battery of the present invention still has better discharge performance under the extreme low temperature conditions (-40 ° C), and maintains the voltage above 2 V in the case of a large current discharge close to 9 C. It can meet the needs of most electronic equipment at low temperatures and can be recharged at this temperature (-40 ° C). As the experimental temperature increases, the discharge of the rechargeable secondary lithium ion battery of the present invention is maintained at a higher operating voltage during the 10-second discharge time of the entire test, especially at high temperatures (85 ° C). It can maintain almost the same discharge performance as at normal temperature, and it can also be recharged at this temperature (85 ° C).

图 7 所示为在本发明的一个实施例中，本发明的一次电池和可充电二次锂离子电池并联形成的电池组件在 -40°C、 25°C和 85°C的温度条件下的脉冲放电数据曲线图。相对于单独的可充电二次锂离子电池，本发明的电池组件在低温范围下也具有较佳的放电性能。即在相同次数（如 10次）的充放电的情况下，在上述的宽的温度范围内的放电性能曲线都比较稳定，大大提高了整个电池组件的性能。由此可见，本发明的电池从根本上解决了困扰在一次电池和可充电二次锂离子电池不能在极限的低温和极限高温的恶劣环境下使用的问题，有利于改善和推动整个电池行业的发展。 Figure 7 is a diagram showing the battery assembly of the primary battery and the rechargeable secondary lithium ion battery of the present invention connected in parallel at temperatures of -40 ° C, 25 ° C and 85 ° C in one embodiment of the present invention. Pulse discharge data graph. The battery module of the present invention also has better discharge performance at a low temperature range with respect to a single rechargeable secondary lithium ion battery. That is, in the case of the same number of times (e.g., 10 times) of charge and discharge, the discharge performance curves in the above wide temperature range are relatively stable, and the performance of the entire battery assembly is greatly improved. It can be seen that the battery of the invention fundamentally solves the problem that the primary battery and the rechargeable secondary lithium ion battery cannot be used in the harsh environment of the extreme low temperature and the extreme high temperature, which is beneficial to improve and promote the whole battery industry. development of.

此外，为提高电池组的电压或功率，还可以对本发明的一次电池和可充电二次锂离子电池进行不同的串联和 /或并联组合。例如，将多个可充电二次锂离子电池串联之后再并联一次电池，或者多个可充电二次锂离子电池串联之后再与多个串联起来的一次电池进行并联等，这些在实际使用中可以根据需要进行选择和组合。值得一提的是，上述的不同组合的电池组都能在上述极限的低温 Further, in order to increase the voltage or power of the battery pack, it is also possible to perform different series and/or parallel combinations of the primary battery and the rechargeable secondary lithium ion battery of the present invention. For example, a plurality of rechargeable secondary lithium ion batteries are connected in series and then connected in parallel, or a plurality of rechargeable secondary lithium ion batteries are connected in series and then connected in parallel with a plurality of primary batteries connected in series, etc., which can be used in actual use. Choose and combine as needed. It is worth mentioning that the above different combinations of battery packs can be at the above-mentioned low temperature.

(-40°0 和极限高温（85°C ) 范围内正常充电放电和正常使用，不会有诸如易然易爆的风险发生。 (Normally charged and discharged and normal use within the range of -40°0 and extreme high temperature (85°C), there is no risk of such an easy explosion.

以上内容是结合具体的实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单推演或替换。应当理解，这些推演或替换都在本发明的权利要求的保护范围之内。 The above is a further detailed description of the present invention in connection with the specific embodiments, and it is not intended that the specific embodiments of the invention are limited to the description. For those skilled in the art, a number of simple deductions or substitutions may be made without departing from the inventive concept. It is to be understood that these derivations or substitutions are within the scope of the appended claims.

Claims

1.可充电二次锂离子电池，包括阴极材料、阳极材料、隔膜和电解液；其特征在于，所述的阳极材料为阳极复合材料，且所述的可充电二次锂离子电池中的所述阴极材料可逆地结合锂离子的容量与所述阳极复合碳^材料以 LiC₆形式可逆地结合锂离子的容量之比在 0.5:1至 2:1之间。 A rechargeable secondary lithium ion battery comprising a cathode material, an anode material, a separator and an electrolyte; wherein the anode material is an anode composite material, and wherein the rechargeable secondary lithium ion battery is The ratio of the capacity of the cathode material to reversibly bind lithium ions to the capacity of the anode composite carbon material to reversibly bind lithium ions in the form of LiC ₆ is between 0.5:1 and 2:1.

2.根据权利要求 1所述的可充电二次锂离子电池，其特征在于，所述阳极复合材料包括复合碳^材料，该复合碳^材料包括基本碳^材料和微结构碳^ 材料，所述基本碳^材料选自石墨、焦炭、炭黑、硬碳、软碳及其组合，所述微结构碳^材料选自石墨烯、石墨烯微片、单层碳纳米管、多层碳纳米管、中间相微球碳、微孔活性碳及其组合。 2 . The rechargeable secondary lithium ion battery according to claim 1 , wherein the anode composite material comprises a composite carbon material, wherein the composite carbon material comprises a basic carbon material and a microstructure carbon material. The basic carbon material is selected from the group consisting of graphite, coke, carbon black, hard carbon, soft carbon, and combinations thereof. The microstructured carbon material is selected from the group consisting of graphene, graphene microchips, single-walled carbon nanotubes, and multilayer carbon nanomaterials. Tube, mesophase microsphere carbon, microporous activated carbon, and combinations thereof.

3.根据权利要求 2所述的可充电二次锂离子电池，其特征在于，所述基本碳^材料的颗粒尺度在 0.5-100微米之间,优选地，所述基本碳^材料的颗粒尺度在 0.8-50微米之间。 The rechargeable secondary lithium ion battery according to claim 2, wherein the basic carbon material has a particle size of between 0.5 and 100 μm, preferably, a particle size of the basic carbon material. Between 0.8-50 microns.

4.根据权利要求 3所述的可充电二次锂离子电池，其特征在于，所述微结构碳^材料相应的微结构尺度小于 2微米；优选地，所述微结构碳 ^材料相应的微结构尺度小于 500纳米。 The rechargeable secondary lithium ion battery according to claim 3, wherein the microstructure of the microstructured carbon material has a microstructure dimension of less than 2 micrometers; preferably, the microstructured carbon material has a corresponding micro The structural scale is less than 500 nanometers.

5.根据权利要求 2所述的可充电二次锂离子电池，其特征在于，其特征在于，所述微结构碳 ^材料在所述复合碳 ^材料中的^量占比在 0.5%-50%之间，优选地，所述微结构碳 ^材料在所述复合碳 ^材料中的^量占比在 3-50%之间。 The rechargeable secondary lithium ion battery according to claim 2, wherein the microstructure carbon material has a ratio of 0.5% to 50% in the composite carbon material. Between %, preferably, the proportion of the microstructured carbon material in the composite carbon material is between 3 and 50%.

6. 根据权利要求 2-5任一所述的可充电二次锂离子电池，其特征在于，所述可充电二次锂离子电池中阳极材料还包含粘合剂和导电剂，所述粘合剂和导电剂相对所述阳极材料的总 ^量占比小于 30%，较佳地，所述粘合剂和导电剂相对所述阳极材料的总^量占比小于 10%。 The rechargeable secondary lithium ion battery according to any one of claims 2 to 5, wherein the anode material in the rechargeable secondary lithium ion battery further comprises a binder and a conductive agent, the bonding The ratio of the total amount of the agent and the conductive agent to the anode material is less than 30%. Preferably, the ratio of the binder and the conductive agent to the total amount of the anode material is less than 10%.

7. 根据权利要求 1所述的可充电二次锂离子电池，其特征在于，所述可充电二次锂离子电池中阴极材料包括锂化过渡金属插层材料，该锂化过渡金属插层材料选自锂化过渡金属氧化物、混合的锂化过渡金属盐和锂化金属磷酸盐的一种或多种。 7. The rechargeable secondary lithium ion battery according to claim 1, wherein the cathode material in the rechargeable secondary lithium ion battery comprises a lithiated transition metal intercalation material, the lithiated transition metal intercalation material One or more selected from the group consisting of lithiated transition metal oxides, mixed lithiated transition metal salts, and lithiated metal phosphates.

8. 根据权利要求 7所述的可充电二次锂离子电池，其特征在于，所述锂化过渡金属插层材料选自 LiCo0₂、 LiNi_xCo_1-x0₂、 LiNi_xAl_1-x0₂、 LiMn_xNi_yCo_z0₂、 LiNi_xCo_yAl_z0₂、 LiMn0₂、 LiFeP0₄及其组合，更优选 LiMn0₂、 LiNi_xCo_yAl_z0₂、 LiNi_xCo_1-x0₂、 LiMn_xNi_yCo_z0₂及其组合。 The rechargeable secondary lithium ion battery according to claim 7, wherein the lithiated transition metal intercalation material is selected from the group consisting of LiCo0 ₂ , LiNi _x Co _1-x 0 ₂ , LiNi _x Al _1-x 0 ₂ , LiMn _x Ni _y Co _z 0 ₂ , LiNi _x Co _y Al _z 0 ₂ , LiMn0 ₂ , LiFeP0 ₄ and combinations thereof, more preferably LiMn0 ₂ , LiNi _x Co _y Al _z 0 ₂ , LiNi _x Co _1-x 0 ₂ , LiMn _x Ni _y Co _z 0 ₂ and combinations thereof.

9. 根据权利要求 7或 8所述的可充电二次锂离子电池，其特征在于，所述锂化过渡金属插层材料中， Co在过渡金属元素中的摩尔比低于 25%。 The rechargeable secondary lithium ion battery according to claim 7 or 8, wherein a molar ratio of Co in the transition metal element is less than 25% in the lithiated transition metal intercalation material.

10. 根据权利要求 1所述的可充电二次锂离子电池，其特征在于，所述可充电二次锂离子电池中的电解液与阳极材料和阴极材料接触并浸渍所述的隔膜，其中，所述电解液包含至少一种相对低粘度的溶剂和至少一种具有相对高介电常数或具有低熔点及高沸点的溶剂，所述相对低粘度溶剂选自四氢呋喃、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、碳酸二丙酯、二乙二醇二甲醚、乙二醇二甲醚，所述具有相对高介电常数或具有低熔点及高沸点的溶剂选自碳酸乙酯、乙酸甲酯、丙酸甲酯、溴甲烷、甲酸甲酯、乙酸乙酯、丙酸乙酯、溴乙烷、碳酸丙烯酯、碳酸丁二醇酯、乙腈、二甲基亚砜、二甲基甲酰胺、 N- 甲基吡咯烷酮及其混合物。 10. The rechargeable secondary lithium ion battery according to claim 1, wherein the electrolyte in the rechargeable secondary lithium ion battery is in contact with the anode material and the cathode material and impregnated into the separator, wherein The electrolyte comprises at least one relatively low viscosity solvent and at least one solvent having a relatively high dielectric constant or having a low melting point and a high boiling point selected from the group consisting of tetrahydrofuran, dimethyl carbonate, and carbonic acid. Ethyl ester, ethyl methyl carbonate, methyl propyl carbonate, dipropyl carbonate, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, the solvent having a relatively high dielectric constant or having a low melting point and a high boiling point Selected from ethyl carbonate, methyl acetate, methyl propionate, methyl bromide, methyl formate, ethyl acetate, ethyl propionate, ethyl bromide, propylene carbonate, butylene carbonate, acetonitrile, dimethyl Sulfone, dimethylformamide, N-methylpyrrolidone and mixtures thereof.

11. 根据权利要求 10所述的可充电二次锂离子电池，其特征在于，所述电解液中至少含有一种具有在循环过程中保护电极表面的添加剂，所述添加剂选自碳酸亚乙烯酯、己烯雌酚、丁磺酸内酯、二甲疏醚中的一种或多种。 The rechargeable secondary lithium ion battery according to claim 10, wherein the electrolyte contains at least one additive having a surface for protecting the electrode during the cycle, and the additive is selected from the group consisting of vinylene carbonate. One or more of diethylstilbestrol, butane sultone, and dimethyl ketone.

12. 根据权利要求 10或 11所述的可充电二次锂离子电池，其特征在于，所述电解液中至少含有一种锂金属盐，所述锂金属盐选自 LiPF₆、 LiBF₄、 LiBOB、 LiTFSI、 LiC10₄及其组合。 The rechargeable secondary lithium ion battery according to claim 10 or 11, wherein the electrolyte contains at least one lithium metal salt, and the lithium metal salt is selected from the group consisting of LiPF ₆ , LiBF ₄ , and LiBOB. , LiTFSI, LiC10 ₄ and combinations thereof.

13. 根据权利要求 10或 11所述的可充电二次锂离子电池，其特征在于，所述电解液包括碳酸乙酯：碳酸二甲酯：碳酸甲乙酯：碳酸二乙酯：乙酸丙酯的混合溶剂体系，并包含溶解于其中的锂金属盐以及添加剂。 The rechargeable secondary lithium ion battery according to claim 10 or 11, wherein the electrolyte comprises ethyl carbonate: dimethyl carbonate: ethyl methyl carbonate: diethyl carbonate: propyl acetate a mixed solvent system and comprising a lithium metal salt dissolved therein and an additive.

14. 根据权利要求 13所述的可充电二次锂离子电池，其特征在于，所述混合溶剂体系中各溶剂在总混合溶剂体系中的摩尔比范围为碳酸乙酯： 5%~55%、碳酸甲乙酯： 1%〜55%、碳酸二乙酯： 3%〜50%、碳酸二甲酯： 5%〜70%、乙酸丙酯： 5%〜60%； The rechargeable secondary lithium ion battery according to claim 13, wherein the molar ratio of each solvent in the mixed solvent system in the total mixed solvent system is ethyl carbonate: 5% to 55%, Ethyl methyl carbonate: 1% to 55%, diethyl carbonate: 3% to 50%, dimethyl carbonate: 5% to 70%, propyl acetate: 5% to 60%;

优选地，所述添加剂相对所述混合溶剂体系的摩尔比范围为 5%〜75%。 Preferably, the molar ratio of the additive to the mixed solvent system ranges from 5% to 75%.

15. 可于宽温度范围提供高放电脉冲的锂电池组件，其特征在于，所述锂电池组件包括： 15. A lithium battery assembly that provides a high discharge pulse over a wide temperature range, wherein the lithium battery assembly comprises:

一次锂 /(¾氧化物电池；以及 Primary lithium / (3⁄4 oxide battery; and

可充电二次锂离子电池，其与所述一次锂 / 1¾氧化物电池并联连接，其中，所述可充电二次锂离子电池中包含阴极材料和阳极复合碳^材料，所述阴极材料可逆地结合锂离子的容量与所述阳极复合碳^材料以 LiC₆形式可逆地结合锂离子的容量之比在 0.5:1至 2:1之间；且所述可充电二次锂离子电池在充满状态下的开路电压高于并联的所述一次锂 / 1¾氧化物电池的开路电压。 a rechargeable secondary lithium ion battery connected in parallel with the primary lithium/13⁄4 oxide battery, wherein the rechargeable secondary lithium ion battery comprises a cathode material and an anode composite carbon material, the cathode material being reversibly The ratio of the capacity of the combined lithium ion to the capacity of the anode composite carbon material to reversibly bind the lithium ion in the form of LiC ₆ is between 0.5:1 and 2:1; And the open circuit voltage of the rechargeable secondary lithium ion battery in the full state is higher than the open circuit voltage of the primary lithium/13⁄4 oxide battery connected in parallel.

16. 根据权利要求 15所述的锂电池组件，其特征在于，所述可充电二次锂离子电池中阳极材料包括复合碳^材料，该复合碳^材料包括基本碳^材料和微结构碳^材料，所述基本碳^材料选自石墨、焦炭、炭黑、硬碳、软碳及其组合，所述微结构碳 ^材料选自石墨烯、石墨烯微片、单层碳纳米管、多层碳纳米管、中间相微球碳、微孔活性碳及其组合。 16. The lithium battery assembly according to claim 15, wherein the anode material in the rechargeable secondary lithium ion battery comprises a composite carbon material comprising a basic carbon material and a microstructure carbon. The material, the basic carbon material is selected from the group consisting of graphite, coke, carbon black, hard carbon, soft carbon, and combinations thereof, the microstructure carbon material selected from the group consisting of graphene, graphene microchips, single-walled carbon nanotubes, and more Layer carbon nanotubes, mesophase microsphere carbon, microporous activated carbon, and combinations thereof.

17. 根据权利要求 16所述的锂电池组件，其特征在于，所述基本碳^材料的颗粒尺度在 0.5-100微米之间,优选地，所述基本碳^材料的颗粒尺度在 0.8-50 微米之间。 The lithium battery assembly according to claim 16, wherein the basic carbon material has a particle size of between 0.5 and 100 μm, and preferably, the basic carbon material has a particle size of 0.8 to 50. Between microns.

18. 根据权利要求 16所述的锂电池组件，其特征在于，所述微结构碳 ^材料相应的微结构尺度小于 2微米；优选地，所述微结构碳 ^材料相应的微结构尺度小于 500纳米。 The lithium battery assembly according to claim 16, wherein the microstructure of the microstructured carbon material has a microstructure dimension of less than 2 micrometers; preferably, the microstructure of the microstructured carbon material has a microstructure dimension of less than 500 Nano.

19. 根据权利要求 16-18任一所述的锂电池组件，其特征在于，所述微结构碳^材料在所述复合碳^材料中的^量占比在 0.5%-50%之间；优选地，所述微结构碳^材料在所述复合碳^材料中的^量占比在 3-50%之间。 The lithium battery assembly according to any one of claims 16 to 18, wherein a ratio of the microstructure carbon material in the composite carbon material is between 0.5% and 50%; Preferably, the proportion of the microstructured carbon material in the composite carbon material is between 3 and 50%.

20. 根据权利要求 16-18任一所述的锂电池组件，其特征在于，所述可充电二次锂离子电池中阳极材料还包含粘合剂和导电剂，所述粘合剂和导电剂相对所述阳极材料的总^量占比小于 30%，较佳地，所述粘合剂和导电剂相对所述阳极材料的总 ^量占比小于 10% o The lithium battery assembly according to any one of claims 16 to 18, wherein the anode material in the rechargeable secondary lithium ion battery further comprises a binder and a conductive agent, the binder and the conductive agent The ratio of the total amount of the anode material is less than 30%. Preferably, the ratio of the binder and the conductive agent to the total amount of the anode material is less than 10%.

21. 根据权利要求 15所述的锂电池组件，其特征在于，所述可充电二次锂离子电池中阴极材料包括锂化过渡金属插层材料，该锂化过渡金属插层材料选自锂化过渡金属氧化物、混合的锂化过渡金属盐和锂化金属磷酸盐的一种或多种。 The lithium battery assembly according to claim 15, wherein the cathode material in the rechargeable secondary lithium ion battery comprises a lithiated transition metal intercalation material selected from the group consisting of lithiated One or more of a transition metal oxide, a mixed lithiated transition metal salt, and a lithiated metal phosphate.

22. 根据权利要求 20所述的锂电池组件，其特征在于，所述锂化过渡金属插层材料选自 LiCo0₂、 LiNi_xCoi_-x0₂、 LiNi_xAl_1-x0₂、 LiMn_xNi_yCo_z0₂、 LiNi_xCo_yAl_z0₂、 LiMn0₂、 LiFeP0₄及其组合，更优选 LiMn0₂、 LiNi_xCo_yAl_z0₂、 LiNi_xCo_1-x0₂、 LiMn_xNi_yCo_z0₂及其组合。 The lithium battery assembly according to claim 20, wherein the lithiated transition metal intercalation material is selected from the group consisting of LiCo0 ₂ , LiNi _x Coi - _x 0 ₂ , LiNi _x Al _1-x 0 ₂ , LiMn _x Ni _y Co _z 0 ₂ , LiNi _x Co _y Al _z 0 ₂ , LiMn0 ₂ , LiFeP0 ₄ and combinations thereof, more preferably LiMn0 ₂ , LiNi _x Co _y Al _z 0 ₂ , LiNi _x Co _1-x 0 ₂ , LiMn _x Ni _y Co _z 0 ₂ and combinations thereof.

23. 根据权利要求 21或 22所述的锂电池组件，其特征在于，所述锂化过渡金属插层材料中， Co在过渡金属元素中的摩尔比低于 25%。 The lithium battery pack according to claim 21 or 22, wherein a molar ratio of Co in the transition metal element is less than 25% in the lithiated transition metal intercalation material.

24. 根据权利要求 15所述的锂电池组件，其特征在于，所述可充电二次锂离子电池中包含与阳极材料和阴极材料接触并浸渍隔膜的电解液，所述电解液包含至少一种相对低粘度的溶剂和至少一种具有相对高介电常数或具有低熔点及高沸点的溶剂，所述相对低粘度溶剂选自四氢呋喃、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、碳酸二丙酯、二乙二醇二甲醚、乙二醇二甲醚，所述具有相对高介电常数或具有低熔点及高沸点的溶剂选自碳酸乙酯、乙酸甲酯、丙酸甲酯、溴甲烷、甲酸甲酯、乙酸乙酯、丙酸乙酯、溴乙烷、碳酸丙烯酯、碳酸丁二醇酯、乙腈、二甲基亚砜、二甲基甲酰胺、 N-甲基吡咯烷酮及其混合物。 The lithium battery pack according to claim 15, wherein the rechargeable secondary lithium ion battery includes an electrolyte that is in contact with the anode material and the cathode material and impregnates the separator, the electrolyte a solvent comprising at least one relatively low viscosity and at least one solvent having a relatively high dielectric constant or having a low melting point and a high boiling point, the relatively low viscosity solvent being selected from the group consisting of tetrahydrofuran, dimethyl carbonate, diethyl carbonate, carbonic acid Methyl ethyl ester, methyl propyl carbonate, dipropyl carbonate, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, the solvent having a relatively high dielectric constant or having a low melting point and a high boiling point is selected from the group consisting of ethyl carbonate Ester, methyl acetate, methyl propionate, methyl bromide, methyl formate, ethyl acetate, ethyl propionate, ethyl bromide, propylene carbonate, butylene glycol carbonate, acetonitrile, dimethyl sulfoxide, dimethyl Carbamide, N-methylpyrrolidone and mixtures thereof.

25. 根据权利要求 24所述的锂电池组件，其特征在于，所述电解液中至少含有一种具有在循环过程中保护电极表面的添加剂，所述添加剂选自碳酸亚乙烯酯、己烯雌酚、丁磺酸内酯、二甲疏醚中的一种或多种。 The lithium battery pack according to claim 24, wherein the electrolyte contains at least one additive having a surface for protecting the electrode during the cycle, and the additive is selected from the group consisting of vinylene carbonate, diethylstilbestrol, and butyl. One or more of sultone and dimethyl ketone.

26. 根据权利要求 24或 25所述的锂电池组件，其特征在于，所述电解液中至少含有一种锂金属盐，所述锂金属盐选自 LiPF₆、 LiBF₄、 LiBOB、 LiTFSI、 LiC10₄及其组合。 The lithium battery pack according to claim 24 or 25, wherein the electrolyte contains at least one lithium metal salt, and the lithium metal salt is selected from the group consisting of LiPF ₆ , LiBF ₄ , LiBOB, LiTFSI, and LiC10. ₄ and its combination.

27. 根据权利要求 24或 25所述的锂电池组件，其特征在于，所述电解液包括碳酸乙酯：碳酸二甲酯：碳酸甲乙酯：碳酸二乙酯：乙酸丙酯的混合溶剂体系，并包含溶解于其中的锂金属盐以及添加剂。 The lithium battery pack according to claim 24 or 25, wherein the electrolytic solution comprises ethyl carbonate: dimethyl carbonate: ethyl methyl carbonate: diethyl carbonate: a mixed solvent system of propyl acetate And contains a lithium metal salt dissolved therein and an additive.

28. 根据权利要求 27所述的锂电池组件，其特征在于，所述混合溶剂体系中各溶剂在总混合溶剂体系中的摩尔比范围为碳酸乙酯： 5%~55%、碳酸甲乙酯： 1%〜55%、碳酸二乙酯： 3%〜50%、碳酸二甲酯： 5%〜70%、乙酸丙酯： 5%〜 60% ; The lithium battery module according to claim 27, wherein the molar ratio of each solvent in the mixed solvent system in the total mixed solvent system is ethyl carbonate: 5% to 55%, ethyl methyl carbonate : 1% ~ 55%, diethyl carbonate: 3% ~ 50%, dimethyl carbonate: 5% ~ 70%, propyl acetate: 5% ~ 60%;

29. 根据权利要求 15所述的锂电池组件，其特征在于，所述的一次电池包括锂 /亚疏酰氯电池或锂 /疏酰氯电池作为一次锂 / (¾氧化物电池； The lithium battery pack according to claim 15, wherein the primary battery comprises a lithium/thionoyl chloride battery or a lithium/oluthoyl chloride battery as a primary lithium / (3⁄4 oxide battery;

优选地，选择工作电压为 3.67V的锂 /亚疏酰氯电池或工作电压为 3.9V的锂 /疏酰氯电池作为一次锂 / (¾氧化物电池。 Preferably, a lithium/thionoyl chloride battery operating at 3.67V or a lithium/oamyl chloride battery operating at 3.9V is selected as the primary lithium/(3⁄4 oxide battery).

30. 可于宽温度范围提供高放电脉冲的锂电池组件的形成方法，其特征在于，所述方法包括： 30. A method of forming a lithium battery assembly that provides a high discharge pulse over a wide temperature range, the method comprising:

将按照应用需求计算类型容量的一次锂 /(¾氧化物电池及可充电二次锂离子电池进行并联连接； A primary lithium / (3⁄4 oxide battery and a rechargeable secondary lithium ion battery) of a type capacity calculated according to the application requirements are connected in parallel;

根据所选择的一次锂 /)¾氧化物电池类型，使可充电二次锂离子电池在充满状态下的开路电压高于并联的一次锂 / 1¾氧化物电池的开路电压；以及 Depending on the type of primary lithium /) 3⁄4 oxide cell selected, the open circuit voltage of the rechargeable secondary lithium ion battery in the fully charged state is higher than the open circuit voltage of the parallel primary lithium / 13⁄4 oxide battery;

使两者并联且负载端开路条件下可充电二次锂离子电池的电压低于充满状态的电压。 The voltage of the rechargeable secondary lithium ion battery is lower than the full load when the two are connected in parallel and the load end is open State voltage.

31. 根据权利要求 30所述的方法，其特征在于，所述方法还包括调整可充电二次锂离子电池中阴极材料和阳极复合碳^材料的比例，使得所述阴极材料可逆地结合锂离子的容量与所述阳极复合碳^材料以 LiC₆形式可逆地结合锂离子的容量之比在 0.5: 1至 2:1之间。 31. The method according to claim 30, further comprising adjusting a ratio of a cathode material and an anode composite carbon material in the rechargeable secondary lithium ion battery such that the cathode material reversibly binds lithium ions The ratio of the capacity to the capacity of the anode composite carbon material to reversibly bind lithium ions in the form of LiC ₆ is between 0.5:1 and 2:1.

32.根据权利要求 30或 31所述的方法，其特征在于，所述方法还包括选择锂 /亚疏酰氯电池或锂 /疏酰氯电池作为一次锂 / (¾氧化物电池； The method according to claim 30 or 31, wherein the method further comprises selecting a lithium/thionoyl chloride battery or a lithium/acid chloride battery as the primary lithium / (3⁄4 oxide battery;