WO2016110127A1 - Negative electrode active material for lithium-ion/sodium-ion battery, negative electrode and battery - Google Patents

Abstract

A negative electrode active material for a lithium-ion/sodium-ion secondary battery, a negative electrode and a battery relate to the technical field of electrochemistry and batteries. The negative electrode active material comprises a phosphorus-germanium compound, or/and a first complex formed by the phosphorus-germanium compound and elementary P or/and elementary Ge, or/and a second complex formed by the phosphorus-germanium compound and conductive components, or/and a third complex formed by the first complex and conductive components. The negative electrode has the advantages of high specific capacity, high initial Coulomb efficiency, small charge-discharge voltage platform difference and good high-current charge-discharge performance.

Description

一种锂离子/钠离子电池用负极活性材料、负极及电池Negative electrode active material for lithium ion/sodium ion battery, negative electrode and battery 【技术领域】[Technical Field]

本发明属于电化学及电池技术领域，更具体地，涉及一种锂离子/钠离子电池用负极活性材料、负极及电池。The invention belongs to the field of electrochemistry and battery technology, and more particularly relates to a negative electrode active material for a lithium ion/sodium ion battery, a negative electrode and a battery.

【背景技术】【Background technique】

与镍氢、镍镉等电池相比，锂离子电池具有电压高、容量高、重量小的特性。因此，近年来，锂二次电池广泛用作移动通信仪器、便携式电子仪器、电动自行车、电动双轮车、电动汽车等的主电源。但是，随着通讯、电动汽车、电子设备和空间技术等方面迅速发展，对电池的性能提出了越来越高的要求，探寻新的能源储存***来克服传统燃料储能***已成为当今一项挑战。可充电锂电池具有价格低、循环寿命长、能量密度高以及优良的可逆性等优点，其已经成为诸多研究的焦点。Lithium-ion batteries have higher voltage, higher capacity, and lower weight than batteries such as nickel-metal hydride and nickel-cadmium. Therefore, in recent years, lithium secondary batteries have been widely used as main power sources for mobile communication instruments, portable electronic instruments, electric bicycles, electric two-wheel vehicles, electric vehicles, and the like. However, with the rapid development of communications, electric vehicles, electronic equipment and space technology, there is an increasing demand for battery performance. Searching for new energy storage systems to overcome traditional fuel energy storage systems has become a challenge. Rechargeable lithium batteries have many advantages such as low price, long cycle life, high energy density and excellent reversibility.

目前，可充电锂离子电池常采用石墨作为负极材料，但是，用于可充电锂电池中的商用石墨负极材料的容量仅为372mA h/g，并且锂离子在石墨中的嵌入电位较低，容易形成锂枝晶，进而造成电池短路，从而带来安全隐患。过渡金属氧化物也可作为电池的负极材料，其比容量能够达到较高水平，大概700-1500mA h/g，但是其首次库伦效率比较低，一般在60％以下，也不适合作商用锂电池负极材料。硅、锗、锡等与锂形成的合金具有较高的容量，但是其首次库伦效率也很难达到80％，应用前景仍然不佳。总之，目前二次锂离子电池中缺乏综合性能优良的负极。At present, rechargeable lithium ion batteries often use graphite as a negative electrode material, but the commercial graphite negative electrode material used in rechargeable lithium batteries has a capacity of only 372 mA h/g, and the lithium ion has a low embedding potential in graphite, which is easy. The formation of lithium dendrites, which in turn causes a short circuit in the battery, poses a safety hazard. The transition metal oxide can also be used as the negative electrode material of the battery, and its specific capacity can reach a high level, about 700-1500 mA h/g, but its first coulombic efficiency is relatively low, generally below 60%, and it is not suitable for commercial lithium battery anode. material. Silicon, tantalum, tin and other alloys formed with lithium have higher capacity, but their first coulombic efficiency is difficult to reach 80%, and the application prospects are still poor. In short, there is currently a lack of a comprehensive negative electrode in a secondary lithium ion battery.

虽然锂离子电池的应用前景十分广泛，但是地壳锂资源比较匮乏，而且分布不均，我国的锂资源更是匮乏。与锂资源相比，地壳中钠资源含量比较丰富，而且我国的钠资源储量很大，因此开发高性能的钠离子电池来 替代锂离子电池成为降低二次电池成本的一条重要途径。目前室温钠离子电池负极材料缺乏，其中具有商业应用前景的硬碳容量仅为200mA h/g。如此低的容量严重限制了钠离子电池的能量密度。因此，目前室温钠离子电池中也缺乏综合性能优良的负极。Although the application prospects of lithium-ion batteries are very extensive, the lithium resources of the crust are scarce and unevenly distributed, and the lithium resources in China are scarce. Compared with lithium resources, the sodium content in the crust is relatively abundant, and China's sodium resources are very large, so the development of high-performance sodium-ion batteries Replacing lithium-ion batteries has become an important way to reduce the cost of secondary batteries. At present, the negative electrode material of sodium ion battery at room temperature is lacking, and the hard carbon capacity with commercial application prospect is only 200 mA h/g. Such low capacity severely limits the energy density of sodium ion batteries. Therefore, at present, a room temperature sodium ion battery also lacks a negative electrode having excellent comprehensive performance.

【发明内容】[Summary of the Invention]

针对现有技术的以上缺陷或改进需求，本发明提供了一种锂离子/钠离子二次电池用负极活性材料、负极及电池，其目的在于提供一种比容量高，首次库伦效率高且充放电电压平台差别小、电压平台适中的适用于锂离子电池和钠离子电池的负极，并提供了包括该种负极的锂离子电池和钠离子电池，由此解决目前锂离子电池以及钠离子电池的负极存在容量不足或者首次库伦效率比较低的技术问题。The present invention provides a negative electrode active material for a lithium ion/sodium ion secondary battery, a negative electrode, and a battery, and aims to provide a high specific capacity, a first coulomb efficiency, and a charge. The discharge voltage platform has small difference and moderate voltage platform, and is suitable for the negative electrode of lithium ion battery and sodium ion battery, and provides a lithium ion battery and a sodium ion battery including the negative electrode, thereby solving the current lithium ion battery and sodium ion battery. There is a technical problem that the negative electrode has insufficient capacity or the first coulombic efficiency is low.

为了实现上述目的，按照本发明的一个方面，提供一种锂离子/钠离子电池用负极活性材料，所述负极活性材料包括：In order to achieve the above object, according to an aspect of the invention, an anode active material for a lithium ion/sodium ion battery is provided, the anode active material comprising:

磷锗化合物；和/或所述磷锗化合物与单质P和/或单质Ge所形成的第一复合物；和/或所述磷锗化合物与导电组元所形成的第二复合物，所述导电组元自身具有导电能力；和/或所述第一复合物与导电组元所形成的第三复合物，其中，所述磷锗化合物包括下列物质的一种或者几种：a phosphonium compound; and/or a first complex formed by the phosphonium compound and elemental P and/or elemental Ge; and/or a second complex formed by the phosphonium compound and a conductive component, The conductive component itself has electrical conductivity; and/or a third composite formed by the first composite and the conductive component, wherein the phosphonium compound comprises one or more of the following:

(i)由P和Ge所形成的二元整比化合物；(i) a binary integer compound formed of P and Ge;

(ii)由P和Ge所形成的二元非整比化合物；(ii) a binary non-ratio compound formed by P and Ge;

(iii)由P和Ge以及元素M共同形成的多元磷锗化合物，M取自Li，Si，Sn，Pb，Zn，Mn，Fe，Co和Cu中的一种或几种。(iii) a multi-component phosphonium compound formed by P and Ge and an element M, and M is one or more selected from the group consisting of Li, Si, Sn, Pb, Zn, Mn, Fe, Co and Cu.

第一复合物可以是过量的Ge或/和P包覆在磷锗化合物的表面，也可以是磷锗化合物包覆在过量的Ge或/和P表面；还可以是磷锗化合物与过量的Ge或/和P所形成的固溶体，也可是单质Ge或/和P掺杂到磷锗化合物中。过量的Ge、P可以为晶态的，也可以是非晶态的，磷锗化合物可以 是晶态的，也可以是非晶态的。The first composite may be an excess of Ge or/and P coated on the surface of the phosphonium compound, or a phosphonium compound coated on an excess of Ge or/and P surface; or a phosphonium compound and an excess of Ge The solid solution formed by or/and P may also be doped with elemental Ge or/and P into the phosphonium compound. Excessive Ge and P may be crystalline or amorphous, and phosphonium compounds may It is crystalline or amorphous.

第二/三复合物不同于一般的物理混合，而是通过高能机械球磨等方式获得的复合物，在该复合物中，活性材料与导电组元均匀充分复合并且具有强烈的相互作用甚至成键，这种复合物的物质结构稳定，颗粒尺寸小，比表面积大，有利于电解液的浸润渗透、以及有利于锂离子/钠离子和电子的传输，同时导电组元还可以缓冲活性成分在充放电过程中的体积膨胀。由于第二/三复合物中含有比较高的导电组元，做电极膜时也可以不再加入导电组分或导电剂，可直接由第二/三复合物与粘结剂混合均匀后涂覆于集流体上。The second/triple composite is different from the general physical mixing, but a composite obtained by high-energy mechanical ball milling or the like, in which the active material is uniformly and fully compounded with the conductive component and has a strong interaction or even a bond. The composite has stable material structure, small particle size and large specific surface area, which is beneficial to the infiltration and penetration of the electrolyte, and facilitates the transport of lithium ions/sodium ions and electrons, and the conductive component can also buffer the active component in the charge. Volume expansion during discharge. Since the second/third composite contains a relatively high conductive component, the conductive component or the conductive agent may not be added when the electrode film is formed, and the second/third composite may be directly mixed with the binder and then coated. On the current collector.

磷锗化合物、第一/二/三复合物用作锂/钠离子电池负极材料时，可以涂敷或直接生长在二维导电基底上如铜箔上，也可以涂覆或直接生长在三位导电基底上，如泡沫镍，碳布/碳纸或者其他的可以作为集流体的三维导电基底，也可以与碳纳米管、纳米金属、石墨烯等混合均匀后抽滤成膜成为具有自支撑结构的集成电极来直接用作锂/钠离子电池负极。When the phosphonium compound and the first/second/three complex are used as the anode material of the lithium/sodium ion battery, they may be coated or directly grown on a two-dimensional conductive substrate such as a copper foil, or may be coated or directly grown in three places. On the conductive substrate, such as foamed nickel, carbon cloth/carbon paper or other three-dimensional conductive substrate which can be used as a current collector, it can also be mixed with carbon nanotubes, nano metal, graphene, etc., and then filtered to form a self-supporting structure. The integrated electrode is used directly as a negative electrode for lithium/sodium ion batteries.

进一步的，其中所述由P和Ge所形成的二元整比化合物包括GeP、GeP₂、GeP₃、GeP₄、GeP₅、Ge₂P₂、Ge₃P、Ge₂P₃以及Ge₃P₄中的一种或者几种。Further, the binary composition compound formed by P and Ge includes GeP, GeP ₂ , GeP ₃ , GeP ₄ , GeP ₅ , Ge ₂ P ₂ , Ge ₃ P, Ge ₂ P _{3 ,} and Ge ₃ P One or several of ₄ .

进一步的，其中所述由P和Ge所形成的二元非整比化合物包括以下物质的一种或者多种：Further, wherein the binary non-ratio compound formed by P and Ge comprises one or more of the following:

(i)化学通式为Ge_1±aP_1±b的化合物，其中0<a≤0.2，且0<b≤0.2；(i) a compound of the general formula Ge _1±a P _1±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

(ii)化学通式为Ge_1±a P_2±b的化合物，其中0<a≤0.2，且0<b≤0.2；(ii) a compound of the formula: Ge _1±a P _2±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

(iii)化学通式为Ge_1±a P_3±b的化合物，其中0<a≤0.2，且0<b≤0.2；(iii) a compound of the general formula Ge _1±a P _3±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

(iv)化学通式为Ge_1±a P_4±b的化合物，其中0<a≤0.2，且0<b≤0.2；(iv) a compound of the formula G _1±a P _4±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

(v)化学通式为Ge_2±a P_2±b的化合物，其中0<a≤0.2，且0<b≤0.2；(v) a compound of the formula G _{2 ± a} P _{2 ± b} , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

(vi)化学通式为Ge_3±a P_1±b的化合物，其中0<a≤0.2，且0<b≤0.2；(vi) a compound of the general formula Ge _3±a P _1±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

(vii)化学通式为Ge_2±a P_3±b的化合物，其中0<a≤0.2，且0<b≤0.2； (vii) a compound of the formula G _{2 ± a} P _{3 ± b} , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

(xiii)化学通式为Ge_1±a P_5±b的化合物，其中0<a≤0.2，且0<b≤0.2；(xiii) a compound of the formula G _1±a P _5±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

(ix)化学通式为Ge_3±a P_4±b的化合物，其中0<a≤0.2，且0<b≤0.2。(ix) A compound having the chemical formula of Ge _3±a P _4±b , wherein 0 < a ≤ 0.2 and 0 < b ≤ 0.2.

作为优选的，所述由P和Ge所形成的二元非整比化合物包括以下物质的一种或者多种：Preferably, the binary non-ratio compound formed by P and Ge comprises one or more of the following:

(i)化学通式为Ge_1±aP_1±b的化合物，其中0<a≤0.15，且0<b≤0.15；(i) a compound of the general formula Ge _1±a P _1±b , wherein 0 < a ≤ 0.15, and 0 < b ≤ 0.15;

(ii)化学通式为Ge_1±a P_2±b的化合物，其中0<a≤0.15，且0<b≤0.15；(ii) a compound of the general formula Ge _1±a P _2±b , wherein 0 < a ≤ 0.15, and 0 < b ≤ 0.15;

(iii)化学通式为Ge_1±a P_3±b的化合物，其中0<a≤0.15，且0<b≤0.15；(iii) a compound of the general formula Ge _1±a P _3±b , wherein 0 < a ≤ 0.15, and 0 < b ≤ 0.15;

(iv)化学通式为Ge_1±a P_4±b的化合物，其中0<a≤0.15，且0<b≤0.15；(iv) a compound of the formula G _1±a P _4±b , wherein 0 < a ≤ 0.15, and 0 < b ≤ 0.15;

(v)化学通式为Ge_2±a P_2±b的化合物，其中0<a≤0.15，且0<b≤0.15；(v) a compound of the formula G _{2 ± a} P _{2 ± b} , wherein 0 < a ≤ 0.15, and 0 < b ≤ 0.15;

(vi)化学通式为Ge_3±a P_1±b的化合物，其中0<a≤0.15，且0<b≤0.15；(vi) a compound of the general formula Ge _3±a P _1±b , wherein 0 < a ≤ 0.15, and 0 < b ≤ 0.15;

(vii)化学通式为Ge_2±a P_3±b的化合物，其中0<a≤0.15，且0<b≤0.15；(vii) a compound of the formula G _{2 ± a} P _{3 ± b} , wherein 0 < a ≤ 0.15, and 0 < b ≤ 0.15;

(viii)化学通式为Ge_1±a P_5±b的化合物，其中0<a≤0.15，且0<b≤0.15；(viii) a compound of the general formula Ge _1±a P _5±b , wherein 0 < a ≤ 0.15, and 0 < b ≤ 0.15;

(ix)化学通式为Ge_3±a P_4±b的化合物，其中0<a≤0.15，且0<b≤0.15。(ix) A compound having the chemical formula of Ge _3±a P _4±b , wherein 0 < a ≤ 0.15 and 0 < b ≤ 0.15.

作为更进一步的优选的，所述由P和Ge所形成的二元非整比化合物包括以下物质的一种或者多种：As a still further preferred, the binary non-ratio compound formed by P and Ge includes one or more of the following:

(i)化学通式为Ge_1±aP_1±b的化合物，其中0<a≤0.1，且0<b≤0.1；(i) a compound of the general formula Ge _1±a P _1±b , wherein 0 < a ≤ 0.1, and 0 < _b ≤ 0.1;

(ii)化学通式为Ge_1±a P_2±b的化合物，其中0<a≤0.1，且0<b≤0.1；(ii) a compound of the formula G _1±a P _2±b , wherein 0 < a ≤ 0.1, and 0 < _b ≤ 0.1;

(iii)化学通式为Ge_1±a P_3±b的化合物，其中0<a≤0.1，且0<b≤0.1；(iii) a compound of the general formula Ge _1±a P _3±b , wherein 0 < a ≤ 0.1, and 0 < _b ≤ 0.1;

(iv)化学通式为Ge_1±a P_4±b的化合物，其中0<a≤0.1，且0<b≤0.1；(iv) a compound of the formula G _1±a P _4±b , wherein 0 < a ≤ 0.1, and 0 < _b ≤ 0.1;

(v)化学通式为Ge_2±a P_2±b的化合物，其中0<a≤0.1，且0<b≤0.1；(v) a compound of the formula G _2±a P _2±b , wherein 0 < a ≤ 0.1, and 0 < _b ≤ 0.1;

(vi)化学通式为Ge_3±a P_1±b的化合物，其中0<a≤0.1，且0<b≤0.1；(vi) a compound of the general formula Ge _3±a P _1±b , wherein 0 < a ≤ 0.1, and 0 < _b ≤ 0.1;

(vii)化学通式为Ge_2±a P_3±b的化合物，其中0<a≤0.1，且0<b≤0.1；(vii) a compound of the formula G _{2 ± a} P _{3 ± b} , wherein 0 < a ≤ 0.1, and 0 < _b ≤ 0.1;

(viii)化学通式为Ge_1±a P_5±b的化合物，其中0<a≤0.1，且0<b≤0.1；(viii) a compound of the formula G _1±a P _5±b , wherein 0 < a ≤ 0.1, and 0 < _b ≤ 0.1;

(ix)化学通式为Ge_3±a P_4±b的化合物，其中0<a≤0.1，且0<b≤0.1。(ix) A compound of the formula G _3±a P _4±b , wherein 0 < a ≤ 0.1 and 0 < _b ≤ 0.1.

进一步的，由P和Ge所形成的二元非整比化合物也包括由P和Ge所形成的整比化合物与过量的单质P和/或Ge所形成的固溶体的一种或者 多种。Further, the binary non-ratio compound formed by P and Ge also includes one of a solid solution formed of a compound of P and Ge and an excess of elemental P and/or Ge. A variety.

进一步的，其中所述第二/三复合物中，所述导电组元的质量为所述第二/三复合物总质量的10％～70％。作为更进一步的优选，其中所述第二/三复合物中，所述导电组元的质量为所述第二/三复合物总质量的20％～60％。导电组元质量占所述第二/三复合物总质量的10％～70％时，第二/三复合物作为电池负极时，电池性能比较好。多次反复的试验还证明，导电组元质量占所述第二/三复合物总质量的20％～60％时，第二/三复合物作为二次电池负极时，电池的性能更优。磷锗化合物作为负极活性材料时，锂离子或钠离子会嵌入电极中，导致负极的体积膨胀，从而使电化学性能大幅度衰减。加入导电组元具有两方面的作用，一方面可以提高其电子的转移；另一方面也可以缓冲体积膨胀从而优化电极结构达到提升电化学性能的目的。Further, in the second/third composite, the conductive component has a mass of 10% to 70% of the total mass of the second/triple composite. In a still further preferred embodiment, wherein the conductive component has a mass of 20% to 60% of the total mass of the second/triple composite. When the quality of the conductive component accounts for 10% to 70% of the total mass of the second/triple composite, when the second/third composite is used as the negative electrode of the battery, the battery performance is better. Repeated tests have also proved that when the quality of the conductive component accounts for 20% to 60% of the total mass of the second/third composite, the performance of the battery is better when the second/third composite is used as the negative electrode of the secondary battery. When a phosphonium compound is used as a negative electrode active material, lithium ions or sodium ions are embedded in the electrode, causing the volume of the negative electrode to expand, thereby greatly attenuating the electrochemical performance. The addition of conductive components has two functions, on one hand, it can improve the transfer of electrons; on the other hand, it can also buffer the volume expansion to optimize the electrode structure to improve the electrochemical performance.

进一步的，所述导电组元包括具有导电能力的活性炭、天然石墨、人造石墨、碳气凝胶、碳纤维、碳纳米管、石墨氧化物、石墨烯、还原石墨烯、炭黑、乙炔黑、金属Ni、金属Cu、化合物RuO₂、化合物TiC、聚苯胺、聚噻吩以及聚吡咯中的一种或者多种。事实上，导电组元只需具有良好的导电性能，即可用于提高活性材料的电化学性能。此处的导电组元还可以是氮、硼、磷、硫的一种或者多种掺杂的碳材料。Further, the conductive component comprises activated carbon having electrical conductivity, natural graphite, artificial graphite, carbon aerogel, carbon fiber, carbon nanotube, graphite oxide, graphene, reduced graphene, carbon black, acetylene black, metal One or more of Ni, metal Cu, compound RuO ₂ , compound TiC, polyaniline, polythiophene, and polypyrrole. In fact, the conductive component only needs to have good electrical conductivity and can be used to improve the electrochemical performance of the active material. The conductive component herein may also be one or more doped carbon materials of nitrogen, boron, phosphorus, sulfur.

按照本发明的另一个方面，还提供一种锂离子/钠离子电池用负极，所述负极包含：集电器和负极活性材料层，所述负极活性材料层形成在所述集电器的至少一个表面上并包含负极活性材料，其中所述负极活性材料为如上所限定的负极活性材料。According to another aspect of the present invention, there is also provided a negative electrode for a lithium ion/sodium ion battery, the negative electrode comprising: a current collector and a negative active material layer, the negative active material layer being formed on at least one surface of the current collector And comprising an anode active material, wherein the anode active material is an anode active material as defined above.

按照本发明的第三个方面，还提供一种锂离子电池，其包含正极、负极、和设置在所述正极和所述负极之间的隔膜，其中所述负极为如上所限定的负极。According to a third aspect of the present invention, there is further provided a lithium ion battery comprising a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode, wherein the negative electrode is a negative electrode as defined above.

按照本发明的第四个方面，还提供一种钠离子电池，其包含正极、负 极、和设置在所述正极和所述负极之间的隔膜，其中所述负极为如上所限定的负极。According to a fourth aspect of the present invention, there is also provided a sodium ion battery comprising a positive electrode and a negative electrode And a separator disposed between the positive electrode and the negative electrode, wherein the negative electrode is a negative electrode as defined above.

总体而言，通过本发明所构思的以上技术方案与现有技术相比，能够取得下列有益效果：In general, the above technical solutions conceived by the present invention can achieve the following beneficial effects compared with the prior art:

1、本发明方法所制备的磷锗化合物同时含有锗和磷，而磷和锗都具有高的储锂/钠活性，因此磷锗化合物具有高的储锂/钠容量，并且，试验证明，磷锗化合物用于锂离子/钠离子电池的负极材料时，其充放电曲线具有充放电压平台差别小，曲线平缓等优点，便于商业化应用。1. The phosphonium compound prepared by the method of the present invention contains both antimony and phosphorus, and both phosphorus and antimony have high lithium/sodium storage activity, so the phosphonium compound has high lithium/sodium storage capacity, and the test proves that phosphorus When the ruthenium compound is used as a negative electrode material for a lithium ion/sodium ion battery, the charge and discharge curve has the advantages of small difference in charge and discharge voltage platform, gentle curve, and the like, and is convenient for commercial application.

2、本发明中的部分磷锗化合物具有类石墨层状结构或者固溶体结构，试验证明，无论是具有类石墨层状结构的磷锗化合物还是固溶体结构的磷锗化合物，其导电性均优于半导体。多元磷锗化合物中还含有锗之外的金属元素，该金属元素一方面可以传导电子，另一方面可以缓冲电极的体积膨胀，有利于提高电池的高倍率和循环寿命等性能。2. The partial phosphonium compound of the present invention has a graphite-like layer structure or a solid solution structure, and the test proves that the conductivity of the phosphonium compound having a graphite-like layer structure or a solid solution structure is superior to that of the semiconductor. . The multi-phosphorus compound also contains a metal element other than cerium, which can conduct electrons on the one hand and buffer the volume expansion of the electrode on the other hand, which is advantageous for improving the high rate and cycle life of the battery.

3、本发明所制备的第一复合物中，过量的锗包覆在磷锗化合物的表面，金属锗具有较高的导电性，同时还可以形成活性材料与电解质之间的稳定界面从而提高电池的循环稳定性，这样的电极具备更高的倍率性能；过量的磷包覆在磷锗化合物表面时可以进一步提高容量，因为磷的储锂/钠容量比锗还高；磷锗化合物与单质磷或/和锗所形成的固溶体具有金属导电性，从而也有助于提高其电化学性能。3. In the first composite prepared by the invention, an excess of ruthenium is coated on the surface of the phosphonium compound, and the metal ruthenium has high conductivity, and at the same time, a stable interface between the active material and the electrolyte can be formed to improve the battery. Cyclic stability, such electrodes have higher rate performance; excessive phosphorus coating on the surface of the phosphonium compound can further increase the capacity, because the lithium storage/sodium capacity of phosphorus is higher than that of strontium; phosphonium compound and elemental phosphorus The solid solution formed by or/and bismuth has metal conductivity, which also contributes to an improvement in its electrochemical performance.

4、本发明所制备的第二/三复合物中，由于导电组元的引入，从而大大的提高了整个电极材料的电子传输能力，同时还增加了比表面积，更有利于电解液的浸润，可缩短锂离子/钠离子传输距离。由于导电组元的引入，磷锗化合物的颗粒尺寸变得更小甚至非晶化，当锂/钠嵌入这样的电极时，体积膨胀变化大大得到了缓冲，这样反复脱嵌不至于使电极材料从集流体上脱落，也不会引起活性材料的粉碎产生的电绝缘，因而避免了循环性能大幅度下降现象。将其中的GeP₅与C形成的第二复合物作为实验电池的负 极，进行电化学循环性能试验时，发现其循环50次后，容量几乎没有衰减，并且其在4A/g的高倍率下，电池仍然保持1400mA h/g的高容量。4. In the second/third composite prepared by the invention, due to the introduction of the conductive component, the electron transporting ability of the entire electrode material is greatly improved, and the specific surface area is also increased, which is more favorable for the electrolyte infiltration. The lithium ion/sodium ion transport distance can be shortened. Due to the introduction of conductive components, the particle size of the phosphonium compound becomes smaller or even amorphized. When lithium/sodium is embedded in such an electrode, the volume expansion change is greatly buffered, so that repeated deintercalation does not cause the electrode material to be removed. The fluid is detached and does not cause electrical insulation caused by the pulverization of the active material, thereby avoiding a drastic reduction in cycle performance. When the second composite formed of GeP ₅ and C was used as the negative electrode of the experimental battery, when the electrochemical cycle performance test was performed, it was found that after 50 cycles, the capacity was hardly attenuated, and at a high magnification of 4 A/g, The battery still maintains a high capacity of 1400mA h/g.

5、本发明电极中磷锗化合物可直接采用将Ge粉和P粉进行球磨得到，球磨方法与传统的高压合成或者磨碎后高温烧结合成法相比，其工艺步骤少，且无需高温操作，方法更简单。5. The phosphonium compound in the electrode of the invention can be directly obtained by ball milling of the Ge powder and the P powder, and the ball milling method has fewer process steps than the conventional high-pressure synthesis or the high-temperature sintering synthesis method after grinding, and does not require high-temperature operation. simpler.

6、将单质P、单质Ge以及单质C进行高能球磨，可制备得到导电组元为C的第二复合物，这种导电组元为C的第二复合物的具体结构为碳包覆的非晶化材料，其可以直接与粘结剂混合以用作电极，不再需要添加导电剂，大大节省了电极的制备流程。6. Performing high-energy ball milling of elemental P, elemental Ge, and elemental C, a second composite having a conductive component of C can be prepared. The specific structure of the second composite of conductive component C is carbon-coated. A crystallization material that can be directly mixed with a binder to serve as an electrode eliminates the need to add a conductive agent, which greatly saves the electrode preparation process.

总之，本发明电极具有理论容量高、首次库伦效率高、充放电电压平台差别小、循环特性优良、寿命长等优点，并且能够维持高放电容量、高库伦效率、高倍率以及较低电压平台，其具有优良电化学性能，是一种很具有潜力的电极，该电极对于实现安全有效、性能稳定的电池而言具有重大意义。并且，本发明电极主要包括Ge、P及由Ge和P组成的化合物，可以采用球磨方式制备，该电极原料丰富、价格低廉、制备方法简单、便于推广以及大规模生产，是一种极具应用潜力的、适用于锂离子电池以及钠离子电池的电极。In summary, the electrode of the present invention has the advantages of high theoretical capacity, high first coulomb efficiency, small difference in charge and discharge voltage platform, excellent cycle characteristics, long life, and the like, and can maintain high discharge capacity, high coulombic efficiency, high magnification, and low voltage platform. It has excellent electrochemical properties and is a promising electrode, which is of great significance for achieving a safe, effective and stable battery. Moreover, the electrode of the invention mainly comprises Ge, P and a compound consisting of Ge and P, and can be prepared by ball milling. The electrode has abundant raw materials, low price, simple preparation method, convenient promotion and large-scale production, and is an extremely application. Potential for electrodes for lithium-ion and sodium-ion batteries.

【附图说明】[Description of the Drawings]

图1是本发明电极中包含的采用球磨方式制备的GeP的X射线衍射图；1 is an X-ray diffraction chart of a GeP prepared by ball milling included in an electrode of the present invention;

图2是本发明电极中包含的采用球磨方式制备的GeP₅的X射线衍射图；2 is an X-ray diffraction diagram of GeP ₅ prepared by ball milling included in the electrode of the present invention;

图3是本发明实施例中GeP₅的能谱图；3 is an energy spectrum diagram of GeP ₅ in the embodiment of the present invention;

图4是本发明实施例中由GeP₅和C形成的第二复合物的能谱图；4 is an energy spectrum diagram of a second composite formed of GeP ₅ and C in an embodiment of the present invention;

图5是本发明实施例中由GeP₅和C形成的第二复合物的面扫面图，该图中(a)、(b)、(c)以及(d)分别为该复合物的SEM图片，锗元素 分布图、磷元素分布图以及碳元素分布图；Figure 5 is a face-scan view of a second composite formed of GeP ₅ and C in an embodiment of the present invention, in which (a), (b), (c), and (d) are SEMs of the composite, respectively. Picture, 锗 element distribution map, phosphorus element distribution map and carbon element distribution map;

图6是本发明实施例中采用球磨方式制备的GeP₅的SEM图；6 is an SEM image of GeP ₅ prepared by ball milling in an embodiment of the present invention;

图7是本发明实施例电极中包含的GeP的储锂性能图；7 is a graph showing the lithium storage performance of GeP contained in an electrode of an embodiment of the present invention;

图8是本发明实施例电极中包含的GeP的储钠性能图；Figure 8 is a graph showing the sodium storage performance of GeP contained in the electrode of the embodiment of the present invention;

图9为本发明实施例电极中包含的GeP₅的储锂性能图；9 is a graph showing the lithium storage performance of GeP ₅ contained in an electrode according to an embodiment of the present invention;

图10为本发明实施例电极中包含的GeP₅的储钠性能图。Figure 10 is a graph showing the sodium storage performance of GeP ₅ contained in an electrode according to an embodiment of the present invention.

【具体实施方式】【detailed description】

为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Further, the technical features involved in the various embodiments of the present invention described below may be combined with each other as long as they do not constitute a conflict with each other.

本发明提供的锂离子/钠离子二次电池用负极活性材料，是一种成分多样化的材料，其主要包含以下四大类材料中的一种或者多种：The negative electrode active material for a lithium ion/sodium ion secondary battery provided by the present invention is a material having various components, and mainly comprises one or more of the following four types of materials:

(1)磷锗化合物；(1) a phosphonium compound;

(2)第一复合物；(2) a first composite;

(3)第二复合物；(3) a second composite;

(4)第三复合物；(4) a third composite;

磷锗化合物包含由P和Ge所形成的二元整比化合物、由P和Ge所形成的二元非整比化合物以及由P和Ge以及元素M共同形成的多元磷锗化合物；第一复合物为磷锗化合物与单质P和/或单质Ge所形成的复合物或者固溶体；第二复合物为所述磷锗化合物与导电组元所形成的复合物；第三复合物为第一复合物与导电组元所形成的复合物。The phosphonium compound comprises a binary integer compound formed of P and Ge, a binary non-ratio compound formed of P and Ge, and a polyphosphonium compound formed by P and Ge and element M; the first complex a composite or solid solution formed by a phosphonium compound and elemental P and/or elemental Ge; a second composite is a complex formed by the phosphonium compound and a conductive component; and the third composite is a first complex and A composite formed by a conductive component.

以下通过实施例对本发明的负极材料进行更具体的说明，但是，本发明并不限定于这些实施例。 The negative electrode material of the present invention will be more specifically described below by way of examples, but the present invention is not limited to these examples.

＜磷锗化合物的实施例＞<Example of phosphonium compound>

(1)由P和Ge所形成的二元整比化合物(1) Binary ratio compound formed by P and Ge

将纯度为99.8％的磷粉和纯度为99.9％的锗加入球磨罐中，采用的球料比为13:1，转速为350～600转/分钟，球磨2-20小时后获得由P和Ge所形成的二元整比化合物。通过调整磷粉和单质锗的质量比，以该球磨方式可制备获得各种由P和Ge所形成的二元整比化合物，经X射线衍射检测物相，该二元整比化合物有以下几种：GeP、GeP2、GeP3、GeP4、GeP5、Ge2P2、Ge3P、Ge2P3以及Ge3P4。根据磷粉和单质锗的质量比以及球磨时间的改变，产物还可能是以上二元整比化合物中多种的混合物，此时，经X射线衍射检测物相，可出现多个物质的相的衍射峰。表1为本发明实施例中的由P和Ge所形成二元整比化合物。该表格中没有将9种二元整比化合物的各种可能的组合情况一一列出，但是不能因此排除表1中没有列出的其他可能组合。Phosphorus with a purity of 99.8% and strontium with a purity of 99.9% were added to the ball mill tank. The ratio of the ball to the material was 13:1, the rotation speed was 350-600 rpm, and the ball was milled for 2-20 hours to obtain P and Ge. The binary integral compound formed. By adjusting the mass ratio of the phosphor powder and the elemental ruthenium, various binary ratio compounds formed by P and Ge can be prepared by the ball milling method, and the phase is detected by X-ray diffraction, and the binary ratio compound has the following Species: GeP, GeP2, GeP3, GeP4, GeP5, Ge2P2, Ge3P, Ge2P3, and Ge3P4. According to the mass ratio of the phosphor powder and the elemental ruthenium and the change of the milling time, the product may also be a mixture of a plurality of the above binary ratio compounds. At this time, the phase of the plurality of substances may be detected by X-ray diffraction. Diffraction peaks. Table 1 shows the binary integer compound formed of P and Ge in the examples of the present invention. The various possible combinations of the nine binary integer compounds are not listed in the table, but other possible combinations not listed in Table 1 cannot be excluded.

图1是本发明电极中包含的采用球磨方式制备的GeP的X射线衍射图，从图中可知，所有的衍射峰都能与标准的PDF卡片(该卡片的编号为44-1125)相对应，说明获得了纯相的GeP。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an X-ray diffraction diagram of a GeP prepared by ball milling in an electrode of the present invention, and it can be seen from the figure that all diffraction peaks can correspond to a standard PDF card (the card number is 44-1125). It is indicated that a pure phase GeP is obtained.

表1 为本发明实施例中部分的由P和Ge所形成二元整比化合物Table 1 is a partial binary ratio compound formed by P and Ge in the embodiment of the present invention.

实施例Example	XRD分析获得的物相Phase obtained by XRD analysis
		实施例1Example 1	GePGeP
实施例2Example 2	GeP2 GeP 2
		实施例3Example 3	GeP3 GeP 3
实施例4Example 4	GeP4 GeP 4
		实施例5Example 5	GeP5 GeP 5
实施例6Example 6	Ge2P2 Ge 2 P 2

实施例7Example 7	Ge3P4 Ge 3 P 4
		实施例8Example 8	Ge2P3 Ge 2 P 3
实施例9Example 9	Ge3PGe 3 P
		实施例10Example 10	GeP4、Ge3P以及GeP5按照质量比为10％、30％以及60％混合GeP 4 , Ge 3 P and GeP 5 are mixed at a mass ratio of 10%, 30% and 60%
实施例11Example 11	Ge3P4、GeP2以及GeP5按照质量比为20％、5％以及75％混合Ge 3 P 4 , GeP 2 and GeP 5 are mixed at a mass ratio of 20%, 5% and 75%

图2是本发明电极中包含的采用球磨方式制备的GeP₅的X射线衍射图，从图中可知，所有的衍射峰都能与标准的PDF卡片(该卡片的编号为24-0455)相对应，说明获得了纯相的GeP₅。2 is an X-ray diffraction diagram of GeP ₅ prepared by ball milling in the electrode of the present invention, and it can be seen from the figure that all diffraction peaks can correspond to a standard PDF card (the number of the card is 24-0455). , indicating that pure phase GeP _{5 was obtained} .

图3是本发明实施例中GeP₅的能谱图，从图中可知，其由元素Ge和P组成，且Ge与P的原子比为1:5，而其他的少量元素如铜，来自于做TEM的铜网，而碳来自于污染碳。3 is an energy spectrum diagram of GeP ₅ in the embodiment of the present invention. It is known from the figure that it is composed of elements Ge and P, and the atomic ratio of Ge to P is 1:5, and other small elements such as copper are derived from Do TEM copper mesh, and carbon comes from contaminated carbon.

图6是本发明实施例中采用球磨方式制备的GeP₅的SEM图，从图中可知GeP₅的形貌为纳米颗粒，该颗粒为由较小的一次颗粒团聚而成的二次颗粒，这样形成的二次颗粒一方面有利于电解液的浸透另一方面还有较高的振实密度，有利于提高整个电极的能量密度。6 is an SEM image of GeP ₅ prepared by ball milling in the embodiment of the present invention, and it is known that the morphology of GeP ₅ is a nanoparticle, which is a secondary particle formed by agglomerating smaller primary particles, such that The formed secondary particles on the one hand facilitate the impregnation of the electrolyte and on the other hand have a higher tap density, which is advantageous for increasing the energy density of the entire electrode.

(2)由P和Ge所形成的二元非整比化合物(2) Binary non-ratio compounds formed by P and Ge

将纯度为99.8％的磷粉和纯度为99.9％的锗加入球磨罐中，采用球料比为15:1，转速为450转/分钟，球磨15小时的方式获得由P和Ge所形成的二元非整比化合物。通过调整磷粉和单质锗的质量比，以该球磨方式即可制备获得由P和Ge所形成的各种二元非整比化合物，该类化合物经过X射线衍射检测分析以及经过扫描电镜自带的面扫描功能进行成分分析，发现该类化合物对应的衍射峰中具有由P和Ge所形成的二元整比化合物的衍射峰、单质磷和单质锗的衍射峰，但是扫描电镜自带的面扫描成分分析功能检测分析，发现单质磷、单质锗均匀分布，说明二元非整比化合物中部 分为固溶体结构。经过定量的成分分析，得知该二元非整比化合物具有的以下几种：Phosphorus with a purity of 99.8% and strontium with a purity of 99.9% were added to the ball mill tank, and the ratio of the ball to the material was 15:1, the rotation speed was 450 rpm, and the ball was milled for 15 hours to obtain the two formed by P and Ge. Non-integral compound. By adjusting the mass ratio of phosphor powder and elemental germanium, various binary non-ratio compounds formed by P and Ge can be prepared by the ball milling method. The compounds are analyzed by X-ray diffraction and analyzed by scanning electron microscopy. The surface scanning function was carried out to analyze the composition, and it was found that the diffraction peaks of the compounds have diffraction peaks of the binary complex compounds formed by P and Ge, and the diffraction peaks of elemental phosphorus and elemental germanium, but the surface of the scanning electron microscope Scanning component analysis function detection and analysis, found that elemental phosphorus, elemental 锗 uniform distribution, indicating the binary non-ratio compound Divided into solid solution structure. After quantitative component analysis, the following two kinds of binary non-ratio compounds are known:

(i)化学通式为Ge_1±aP_1±b的化合物，其中0<a≤0.2，且0<b≤0.2，其中，高能球磨方式制备后，根据试验分析，证实有Ge_0.8P_1.2、Ge_1.2P_0.8以及Ge_1.2P_1.2；(i) a compound of the formula: Ge _1±a P _1±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2, wherein, after preparation by a high-energy ball milling method, Ge _0.8 P _{1.2 is} confirmed according to experimental analysis. , Ge _1.2 P _0.8 and Ge _1.2 P _1.2 ;

(ii)化学通式为Ge_1±aP_2±b的化合物，其中0<a≤0.2，且0<b≤0.2，其中，高能球磨方式制备后，根据试验分析，证实有Ge_0.8P_2.2、Ge_1.2P_1.8以及Ge₁P_1.9；(ii) a compound of the formula: Ge _1±a P _2±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2, wherein, after preparation by a high-energy ball milling method, Ge _0.8 P _{2.2 is} confirmed according to experimental analysis. , Ge _1.2 P _1.8 and Ge ₁ P _1.9 ;

(iii)化学通式为Ge_1±a P_3±b的化合物，其中0<a≤0.2，且0<b≤0.2，其中，高能球磨方式制备后，根据试验分析，证实有Ge_0.8P_3.2、Ge_1.2P_2.8以及Ge₁P_2.9；(iii) a compound of the formula: Ge _1±a P _3±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2, wherein after preparation by high energy ball milling, according to experimental analysis, it is confirmed that Ge _0.8 P _3.2 , Ge _1.2 P _2.8 and Ge ₁ P _2.9 ;

(iv)化学通式为Ge_1±a P_4±b的化合物，其中0<a≤0.2，且0<b≤0.2，其中，高能球磨方式制备后，根据试验分析，证实有Ge_0.8P_4.2、Ge_1.2P_3.8以及Ge₁P_3.9；(iv) a compound of the formula: Ge _1±a P _4±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2, wherein, after preparation by a high-energy ball milling method, Ge _0.8 P _{4.2 is} confirmed according to experimental analysis. , Ge _1.2 P _3.8 and Ge ₁ P _3.9 ;

(v)化学通式为Ge_2±a P_2±b的化合物，其中0<a≤0.2，且0<b≤0.2，其中，高能球磨方式制备后，根据试验分析，证实有Ge_1.8P_2.2、Ge_2.2P_1.8以及Ge_1.9P_2.1；(v) a compound of the formula: Ge _2±a P _2±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2, wherein, after preparation by a high-energy ball milling method, Ge _1.8 P _{2.2 is} confirmed according to experimental analysis. , Ge _2.2 P _1.8 and Ge _1.9 P _2.1 ;

(vi)化学通式为Ge_3±a P_1±b的化合物，其中0<a≤0.2，且0<b≤0.2，其中，高能球磨方式制备后，根据试验分析，证实有Ge_2.8P_1.2、Ge_3.2P_0.8以及Ge_2.9P_1.1；(vi) a compound of the formula: Ge _3±a P _1±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2, wherein, after preparation by a high-energy ball milling method, Ge _2.8 P _{1.2 is} confirmed according to experimental analysis. , Ge _3.2 P _0.8 and Ge _2.9 P _1.1 ;

(vii)化学通式为Ge_2±a P_3±b的化合物，其中0<a≤0.2，且0<b≤0.2，其中，高能球磨方式制备后，根据试验分析，证实有Ge_1.8P_3.2、Ge_2.2P_2.8以及Ge_1.9P_3.1；(vii) a compound of the general formula Ge _2±a P _3±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2, wherein after preparation by high energy ball milling, according to experimental analysis, it is confirmed that Ge _1.8 P _3.2 , Ge _2.2 P _2.8 and Ge _1.9 P _3.1 ;

(xiii)化学通式为Ge_1±a P_5±b的化合物，其中0<a≤0.2，且0<b≤0.2，其中，高能球磨方式制备后，根据试验分析，证实有Ge_0.8P_5.2、Ge_1.2P_4.8以及Ge_0.9P_5.1； (xiii) a compound having a chemical formula of Ge _1±a P _5±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2, wherein, after preparation by a high-energy ball milling method, Ge _0.8 P _{5.2 is} confirmed according to experimental analysis. , Ge _1.2 P _4.8 and Ge _0.9 P _5.1 ;

(ix)化学通式为Ge_3±a P_4±b的化合物，其中0<a≤0.2，且0<b≤0.2，其中，高能球磨方式制备后，根据试验分析，证实有Ge_2.8P_4.2、Ge_3.2P_3.8以及Ge_2.9P_4.1；(ix) a compound having a chemical formula of Ge _3±a P _4±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2, wherein, after preparation by a high-energy ball milling method, Ge _2.8 P _{4.2 is} confirmed according to experimental analysis. , Ge _3.2 P _3.8 and Ge _2.9 P _4.1 ;

表2为本发明实施例中由P和Ge所形成的二元非整比化合物，该表格中，并没将二元非整比化合物中的各种可能的配比一一列出来，但是不能因此排除表2中没有列出的其他可能的配比。Table 2 is a binary non-ratio compound formed by P and Ge in the embodiment of the present invention. In the table, various possible ratios in the binary non-ratio compound are not listed one by one, but not Therefore, other possible ratios not listed in Table 2 are excluded.

(3)由P和Ge以及元素M共同形成的多元磷锗化合物(3) a multi-component phosphonium compound formed by P and Ge and element M

制备时候，将磷粉、锗以及一种或几种的Li单质、Si粉、Sn粉、Pb单质、Zn单质、Mn单质、Fe粉、Co粉和Cu粉中混合在一起，将其加入球磨罐中，充入氩气保护，采用球料比为20：1，转速为500转/分钟，球磨20小时制备获得该多元磷锗化合物。At the time of preparation, phosphorus powder, bismuth and one or more of Li elemental substance, Si powder, Sn powder, Pb elemental substance, Zn elemental substance, Mn elemental substance, Fe powder, Co powder and Cu powder are mixed together and added to the ball mill. The can was filled with argon gas to obtain the polyphosphorus compound by a ball to ball ratio of 20:1, a rotation speed of 500 rpm, and ball milling for 20 hours.

表2 本发明实施例中由P和Ge所形成的二元非整比化合物Table 2 Binary non-ratio compounds formed by P and Ge in the examples of the present invention

经过X射线衍射检测分析以及经过扫描电镜自带的面扫描功能的成分分析，可知，多元磷锗化合物的化学式为：Li₅GeP₃、ZnGeP₂、MnGeP₂、Zn_1-xMn_xGeP₂，多元磷锗化合物还可以是CdGeP₂、GexPxS_1-2x、Cd_1-xMn_xGeP₂、Zn_1-xMn_xGeP₂。表3列出了部分由P和Ge以及元素M共同形成的多元磷锗化合物。该表中仅仅列出了有限的几种多元磷锗化合物，但是并不能因此将其他没有列出的三元磷锗化合物排除在外。After X-ray diffraction analysis and component analysis of the surface scanning function of the scanning electron microscope, it is known that the chemical formula of the multi-phosphorus compound is: Li ₅ GeP ₃ , ZnGeP ₂ , MnGeP ₂ , Zn _1-x Mn _x GeP ₂ , The polyphosphonium compound may also be CdGeP ₂ , GexPxS _1-2x , Cd _1-x Mn _x GeP ₂ , Zn _1-x Mn _x GeP ₂ . Table 3 lists the polyphosphorus compounds partially formed by P and Ge together with the element M. Only a limited number of polyphosphonium compounds are listed in this table, but other ternary phosphonium compounds not listed are not excluded.

表3 部分由P和Ge以及元素M共同形成的多元磷锗化合物Table 3 Partially composed of P and Ge and element M

实施例Example	XRD分析获得的物相Phase obtained by XRD analysis
		实施例36Example 36	Li5GeP3 Li 5 GeP 3
实施例37Example 37	ZnGeP2 ZnGeP 2
		实施例38Example 38	MnGeP2 MnGeP 2
实施例39Example 39	Zn1-xMnxGeP2 Zn 1-x Mn x GeP 2

＜第一复合物实施例＞<First Composite Example>

表4 部分第一复合物的组成及质量百分比Table 4 Composition and mass percentage of part of the first composite

                           单位：wt.％Unit: wt.%

实施例Example	GePGeP	GeP2 GeP 2	GeP3 GeP 3	GeP5 GeP 5	单质PElemental P	单质GeElemental Ge
							实施例40Example 40	//	//	//	8080	2020	//
实施例41Example 41	//	//	//	7070	//	3030
							实施例42Example 42	3030	5050	//	1010	55	55
实施例43Example 43	2020	//	//	//	8080	//
							实施例44Example 44	2525	//	//	3030	//	4545

实施例45Example 45	//	//	4040	1010	3030	2020
							实施例46Example 46	5050	88	1010	//	2020	1212
实施例47Example 47	22	33	55	6060	//	3030

将以上制备获得的磷锗化合物与纯度为99.8％的磷粉或/和纯度为99.9％的锗加入球磨罐中，采用球料比为18:1，转速为700转/分钟，球磨19小时获得第一复合物。经过X射线衍射检测分析以及经过扫描电镜自带的面扫描功能进行成分分析，发现衍射峰中具有单质磷、单质锗的峰，并且还具有以上所述的磷锗化合物的峰。The phosphonium compound prepared above was added to a ball mill tank with a phosphor powder having a purity of 99.8% or a purity of 99.9%, and a ball-to-feed ratio of 18:1, a rotation speed of 700 rpm, and a ball milling time of 19 hours. First complex. After X-ray diffraction detection analysis and surface scanning function carried out by scanning electron microscopy, component analysis was carried out, and it was found that the diffraction peak had a peak of elemental phosphorus and elemental ruthenium, and also had a peak of the above-mentioned phosphonium compound.

表4为部分第一复合物，表中仅仅列出了几种第一复合物，但是并不能因此将其他没有列出的第一复合物排除在外。Table 4 is a partial first composite in which only a few first complexes are listed, but other first compounds not listed are therefore not excluded.

＜第二复合物实施例＞<Second Composite Example>

将以上制备获得的磷锗化合物与导电组元混合后加入球磨罐中，采用的球料比为19:1，确定转速为400转/分钟，球磨10小时获得第二复合物。其中，导电组元可为具有导电能力的活性炭、天然石墨、石墨烯、石墨片、人造石墨、碳气凝胶、碳纤维、碳纳米管、石墨氧化物，石墨烯，还原石墨烯、导电炭黑、乙炔黑、金属Ni、金属Cu、化合物RuO₂、化合物TiC、聚苯胺、聚噻吩以及聚吡咯，或者是氮、硼、磷、硫中一种或者多种掺杂的碳材料。The phosphonium compound obtained by the above preparation was mixed with a conductive component and then added to a ball mill tank at a ball-to-batch ratio of 19:1, a rotation speed of 400 rpm was determined, and a second composite was obtained by ball milling for 10 hours. The conductive component may be activated carbon having electrical conductivity, natural graphite, graphene, graphite flakes, artificial graphite, carbon aerogel, carbon fiber, carbon nanotubes, graphite oxide, graphene, reduced graphene, conductive carbon black , acetylene black, metal Ni, metal Cu, compound RuO ₂ , compound TiC, polyaniline, polythiophene, and polypyrrole, or one or more doped carbon materials of nitrogen, boron, phosphorus, sulfur.

表5为部分第二复合物，表中仅仅列出了几种第二复合物，但是并不能因此将其他没有列出的第二复合物排除在外。表6中列出了几种导电组元的成分和尺寸，但是并不能因此将该表中没有列的组元和成分排除在外。事实上，导电组元只需具有良好的导电性能，用于电子的传导即可用于提高活性材料的电化学性能。此处的导电组元还可以是氮、硼、磷、硫的一 种或者多种掺杂的碳材料或者是本发明中没有提及的其他具有导电能力的物质。Table 5 is a partial second composite in which only a few second composites are listed, but other secondary compounds not listed are therefore not excluded. The composition and size of several conductive components are listed in Table 6, but the components and components not listed in the table are therefore not excluded. In fact, the conductive component only needs to have good electrical conductivity, and the conduction for electrons can be used to improve the electrochemical performance of the active material. The conductive component here may also be a nitrogen, boron, phosphorus, sulfur one The one or more doped carbon materials are other materials having electrical conductivity not mentioned in the present invention.

表5 部分第二复合物的组成及质量百分比Table 5 Composition and mass percentage of part of the second composite

                               单位：wt.％Unit: wt.%

实施例Example	GePGeP	GeP2 GeP 2	GeP3 GeP 3	GeP5 GeP 5	导电组元Conductive component
						实施例48Example 48	//	55	2525	6060	1010
实施例49Example 49	7070	55	55	//	2020
						实施例50Example 50	//	55	6565	//	3030
实施例51Example 51	55	55	//	7070	2020
						实施例52Example 52	1010	4040	//	//	5050
实施例53Example 53	2020	55	//	1515	6060
						实施例54Example 54	2020	1010	//	//	7070
实施例55Example 55	2525	1010	//	3030	3535
						实施例56Example 56	//	3030	//	1010	6060
实施例57Example 57	1010	1010	1010	55	6565
						实施例58Example 58	22	33	55	4040	5050

表5为部分第二复合物，表中仅仅列出了几种第二复合物，但是并不能因此将其他没有列出的第二复合物排除在外。表6中列出了几种导电组元的成分和尺寸，但是并不能因此将该表中没有列的组元和成分排除在外。事实上，导电组元只需具有良好的导电性能，用于电子的传导即可用于提高活性材料的电化学性能。此处的导电组元还可以是氮、硼、磷、硫的一种或者多种掺杂的碳材料或者是本发明中没有提及的其他具有导电能力的物质。 Table 5 is a partial second composite in which only a few second composites are listed, but other secondary compounds not listed are therefore not excluded. The composition and size of several conductive components are listed in Table 6, but the components and components not listed in the table are therefore not excluded. In fact, the conductive component only needs to have good electrical conductivity, and the conduction for electrons can be used to improve the electrochemical performance of the active material. The conductive component herein may also be one or more doped carbon materials of nitrogen, boron, phosphorus, sulfur or other electrically conductive materials not mentioned in the present invention.

表6 部分导电组元的成分和含量Table 6 Composition and content of some conductive components

图4是本发明实施例中由GeP₅和C形成的第二复合物的能谱图，从图中可知，其包含元素Ge、P、C，而其他的少量元素，如铜来自于做TEM的铜网。4 is an energy spectrum diagram of a second composite formed of GeP ₅ and C in the embodiment of the present invention, which shows that the element contains Ge, P, and C, and other small elements such as copper are derived from TEM. Copper net.

图5是本发明实施例中由GeP₅和C形成的第二复合物的面扫面图，该图中(a)、(b)、(c)以及(d)分别为该复合物的SEM图片，锗元素分布图、磷元素分布图以及碳元素分布图，从图中可知，碳元素与GeP₅化合物均匀混合，且整体呈现出非晶态的特点。Figure 5 is a face-scan view of a second composite formed of GeP ₅ and C in an embodiment of the present invention, in which (a), (b), (c), and (d) are SEMs of the composite, respectively. The picture, the elemental distribution map, the phosphorus element distribution map and the carbon element distribution map, it can be seen from the figure that the carbon element and the GeP ₅ compound are uniformly mixed, and the whole exhibits an amorphous state.

＜第三复合物实施例＞<Third Composite Example>

将第一复合物与导电组元进行球磨，还能得到第三复合物，表7中列 出了部分的第三复合物的成分和含量，该表中仅仅给出了几种第三复合物，但是并不能因此将表中没有列出的其他第三复合物排出在外。并且，该表格中导电组元的质量百分数、磷锗化合物的质量百分数、单质P的质量百分数以及单质Ge的质量百分数之和为100％。The first composite and the conductive component are ball milled, and the third composite is also obtained, and the column in Table 7 Part of the composition and content of the third composite is shown, only a few third composites are given in the table, but other third composites not listed in the table can not be discharged. Further, the sum of the mass percentage of the conductive component, the mass percentage of the phosphonium compound, the mass percentage of the elemental P, and the mass percentage of the elemental Ge in the table is 100%.

表7 部分第三复合物的成分和含量Table 7 Composition and content of some third complexes

                                单位：wt.％Unit: wt.%

实施例Example	GePGeP	GeP2 GeP 2	GeP3 GeP 3	GeP5 GeP 5	单质PElemental P	单质GeElemental Ge	导电组元Conductive component
								实施例59Example 59	//		//	7070	1010	//	天然石墨Natural graphite
实施例60Example 60	//	//	//	7070		1010	人造石墨Artificial graphite
								实施例61Example 61	33	55	//	55	55	55	石墨氧化物Graphite oxide
实施例62Example 62	2020	//	//	//	//	//	金属NiMetal Ni
								实施例63Example 63	2525	//	//	3030	//	//	金属CuMetal Cu
实施例64Example 64	//	//	//	1010	3030	//	还原石墨烯Reduced graphene
								实施例65Example 65	//	88	1010	//	//	1212	聚噻吩Polythiophene
实施例66Example 66	22	33	55	//	//	3030	聚吡咯Polypyrrole

采用本发明负极活性材料制备锂离子或者钠离子二次电池负极，该负极包括集电器和负极活性材料层，负极活性材料层形成在集电器的4个表面上，但是本发明中对负极活性材料层形成在集电器的表面数量不进行具体限定，负极活性材料层中包含有磷锗化合物、第一复合物、第二复合物以及第三复合物中的一种或者多种。A lithium ion or sodium ion secondary battery negative electrode is prepared by using the negative electrode active material of the present invention, the negative electrode includes a current collector and a negative electrode active material layer, and the negative electrode active material layer is formed on four surfaces of the current collector, but the negative electrode active material in the present invention The number of layers formed on the surface of the current collector is not particularly limited, and the negative electrode active material layer contains one or more of a phosphonium compound, a first composite, a second composite, and a third composite.

本发明中，采用GeP作为负极活性材料制备的负极进行电化学性能测试，获得其储锂和储钠的充放电曲线，如图7和图8所示，图7是本发明实施例中以GeP为活性材料制备的电极中的的储锂性能图，从图中可知，其储锂容量约为1897mA h/g，其具有90％以上的首次库伦效率。图8是本 发明实施例中以GeP为活性材料制备的电极中的储钠性能图，从图中可知，其储钠容量约为850mA h/g，其具有接近90％的首次库伦效率。In the present invention, the negative electrode prepared by using GeP as the negative electrode active material is subjected to electrochemical performance test to obtain a charge and discharge curve of lithium storage and sodium storage, as shown in FIG. 7 and FIG. 8, FIG. 7 is a GeP in the embodiment of the present invention. The lithium storage performance map of the electrode prepared for the active material, as shown in the figure, has a lithium storage capacity of about 1897 mA h/g, which has a first coulombic efficiency of 90% or more. Figure 8 is this In the examples of the invention, the sodium storage performance of the electrode prepared by using GeP as an active material shows that the sodium storage capacity is about 850 mA h/g, which has a first coulombic efficiency of nearly 90%.

本发明中，采用GeP₅作为负极活性材料制备的负极进行电化学性能测试，获得其储锂和储钠的充放电曲线，如图9和图10所示，图9是本发明实施例中以GeP₅为活性材料制备的电极的储锂性能图，从图中可知，其储锂容量约为2289mA h/g，其具有90％以上的首次库伦效率。图10是本发明实施例中以GeP₅为活性材料制备的电极的储钠性能图，从图中可知，其储钠容量约为1250mA h/g，其具有接近90％的首次库伦效率。In the present invention, the negative electrode prepared by using GeP ₅ as the negative electrode active material is subjected to electrochemical performance test to obtain a charge and discharge curve of lithium storage and sodium storage, as shown in FIG. 9 and FIG. 10, and FIG. 9 is an embodiment of the present invention. GeP ₅ is a lithium storage performance diagram of an electrode prepared from an active material. As can be seen from the figure, the lithium storage capacity is about 2289 mA h/g, which has a first coulombic efficiency of more than 90%. FIG. 10 is a graph showing the sodium storage performance of an electrode prepared by using GeP ₅ as an active material in the embodiment of the present invention. As can be seen from the figure, the sodium storage capacity is about 1250 mA h/g, which has a first coulombic efficiency close to 90%.

表8列出了部分磷锗化合物和部分第二复合物作为电极活性材料制备的电极的储锂容量。从该表中可知，在磷锗化合物中GeP₅的储锂容量最大，达到大约2289mA h/g，并且，在第二复合物中，GeP₅与C形成的复合物的储锂容量最大，达到大约2389mA h/g。该表中仅仅给了有限的几种锗化合物和有限的几种第二复合物，但是并不能因此将没有列出的其他磷锗化合物和其他的第二复合物排除在外。Table 8 lists the lithium storage capacity of an electrode prepared by using a part of the phosphonium compound and a part of the second composite as an electrode active material. As can be seen from the table, the lithium storage capacity of GeP _{5 is} the largest in the phosphonium compound, reaching about 2289 mA h/g, and in the second composite, the complex of GeP ₅ and C has the largest lithium storage capacity. Approximately 2389 mA h/g. Only a limited number of bismuth compounds and a limited number of second complexes were given in this table, but other phosphonium compounds not listed and other second complexes could not be excluded.

表9列出了部分磷锗化合物和部分第二复合物作为电极活性材料制备的电极的储钠容量。从该表中可知，在磷锗化合物中GeP₅的储钠容量最大，达到1250mA h/g，并且，在第二复合物中，GeP₅与C形成的复合物的储钠容量最大，达到大约1300mA h/g。该表中仅仅给了有限的几种磷锗化合物和有限的几种第二复合物，但是并不能因此将没有列出的其他磷锗化合物和其他的第二复合物排除在外。Table 9 lists the sodium storage capacity of an electrode prepared by using a part of the phosphonium compound and a part of the second composite as an electrode active material. As can be seen from the table, the sodium storage capacity of GeP _{5 is} the largest in the phosphonium compound, reaching 1250 mA h/g, and in the second composite, the complex formed by GeP ₅ and C has the largest sodium storage capacity, reaching approximately 1300 mA h/g. Only a limited number of phosphonium compounds and a limited number of second complexes were given in this table, but other phosphonium compounds not listed and other second complexes could not be excluded.

表8 部分磷锗化合物和部分第二复合物作为电极活性材料制备的电极的储锂容量。Table 8 Lithium storage capacity of an electrode prepared by using a partially phosphonium compound and a part of a second composite as an electrode active material.

表9 部分磷锗化合物和部分第二复合物作为电极活性材料制备的电极的储钠容量Table 9 Sodium storage capacity of electrodes prepared from partial phosphonium compounds and partial second composites as electrode active materials

采用以上电极制备的锂离子或者钠离子电池，包含正极、负极、和设置在所述正极和所述负极之间的隔膜，其中所述负极为如上所限定的负极，该负极包含磷锗化合物、第一复合物、第二复合物以及第三复合物，即，只要包含以上电极的钠离子电池或者锂离子电池，均属于本发明要求保护的范围，只要电极中包含以上的磷锗化合物、第一复合物、第二复合物以及第三复合物均属于本发明要求保护的范围。A lithium ion or sodium ion battery prepared by using the above electrode, comprising a positive electrode, a negative electrode, and a separator disposed between the positive electrode and the negative electrode, wherein the negative electrode is a negative electrode as defined above, the negative electrode comprising a phosphonium compound, The first composite, the second composite, and the third composite, that is, a sodium ion battery or a lithium ion battery including the above electrode, are within the scope of the present invention as long as the electrode contains the above phosphonium compound, A composite, a second composite, and a third composite are all within the scope of the claimed invention.

本发明实施例中，对于导电组元的尺寸、导电组元的具体成分、以及导电组元与化合物的具体配比与组合、或者化合物与单质P或者单质Ge的具体配比以及组合不限于以上具体的实施例，事实上，本发明实施例中导电组元为优选的，还可以选用其他导电性的物质，导电组元的尺寸还可以更小或更大，原则上均可行，并且所述导电组元的质量占所述第二/三复合物总质量的10％～70％，均是可行的，并限定为以上实施例中的具体数值。多次反复的试验还证明，导电组元质量占所述第二/三复合物总质量的20％～60％时，第二/三复合物作为二次电池负极时，电池的性能更优。本发明电极中，对化合物、第一复合物、第二复合以及第三复合物中的具体配比不进行限定。In the embodiment of the present invention, the specific ratio and combination of the size of the conductive component, the specific component of the conductive component, and the specific component and the combination of the conductive component and the compound, or the specific ratio and combination of the compound and the elemental P or the elemental Ge are not limited to the above. Specific embodiments, in fact, in the embodiment of the present invention, the conductive component is preferred, and other conductive materials may also be selected, and the size of the conductive component may be smaller or larger, in principle, and the The mass of the conductive component is 10% to 70% of the total mass of the second/triple composite, and is feasible and limited to the specific values in the above embodiments. Repeated tests have also proved that when the quality of the conductive component accounts for 20% to 60% of the total mass of the second/third composite, the performance of the battery is better when the second/third composite is used as the negative electrode of the secondary battery. In the electrode of the present invention, the specific ratio of the compound, the first composite, the second composite, and the third composite is not limited.

本领域的技术人容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。 It is to be understood by those skilled in the art that the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, any modifications, equivalent substitutions and improvements made within the spirit and scope of the present invention, All should be included in the scope of protection of the present invention.

Claims (10)

1. 一种锂离子/钠离子电池用负极活性材料，所述负极活性材料包括：An anode active material for a lithium ion/sodium ion battery, the anode active material comprising:

   磷锗化合物、Phosphonium compound,

   所述磷锗化合物与单质P和/或单质Ge所形成的第一复合物、a first complex formed by the phosphonium compound and elemental P and/or elemental Ge,

   所述磷锗化合物与导电组元所形成的第二复合物、a second composite formed by the phosphonium compound and the conductive component,

   所述第一复合物与导电组元所形成的第三复合物中的一种或者多种，所述导电组元自身具有导电能力，One or more of the first composite and the third composite formed by the conductive component, the conductive component itself having electrical conductivity,

   其中，所述磷锗化合物包括下列物质的一种或者几种：Wherein the phosphonium compound comprises one or more of the following substances:

   (i)由P和Ge所形成的二元整比化合物；(i) a binary integer compound formed of P and Ge;

   (ii)由P和Ge所形成的二元非整比化合物；(ii) a binary non-ratio compound formed by P and Ge;

   (iii)由P和Ge以及元素M共同形成的多元磷锗化合物，M取自Li，Si，Sn，Pb，Zn，Mn，Fe，Co和Cu中的一种或几种。(iii) a multi-component phosphonium compound formed by P and Ge and an element M, and M is one or more selected from the group consisting of Li, Si, Sn, Pb, Zn, Mn, Fe, Co and Cu.
2. 如权利要求1所述的一种锂离子/钠离子电池用负极活性材料，其中所述由P和Ge所形成的二元整比化合物包括GeP、GeP₂、GeP₃、GeP₄、GeP₅、Ge₂P₂、Ge₂P₃、Ge₃P以及Ge₃P₄中的一种或者几种。The negative electrode active material for a lithium ion/sodium ion battery according to claim 1, wherein the binary integer compound formed of P and Ge comprises GeP, GeP ₂ , GeP ₃ , GeP ₄ , GeP ₅ , One or more of Ge ₂ P ₂ , Ge ₂ P ₃ , Ge ₃ P, and Ge ₃ P ₄ .
3. 如权利要求1所述的一种锂离子/钠离子电池用负极活性材料，其中所述由P和Ge所形成的二元非整比化合物包括以下物质的一种或者多种：The negative electrode active material for a lithium ion/sodium ion battery according to claim 1, wherein the binary non-ratio compound formed of P and Ge comprises one or more of the following:

   (i)化学通式为Ge_1±aP_1±b的化合物，其中0<a≤0.2，且0<b≤0.2；(i) a compound of the general formula Ge _1±a P _1±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

   (ii)化学通式为Ge_1±aP_2±b的化合物，其中0<a≤0.2，且0<b≤0.2；(ii) a compound of the formula: Ge _1±a P _2±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

   (iii)化学通式为Ge_1±aP_3±b的化合物，其中0<a≤0.2，且0<b≤0.2；(iii) a compound of the general formula Ge _1±a P _3±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

   (iv)化学通式为Ge_1±aP_4±b的化合物，其中0<a≤0.2，且0<b≤0.2；(iv) a compound of the formula G _1±a P _4±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

   (v)化学通式为Ge_2±aP_2±b的化合物，其中0<a≤0.2，且0<b≤0.2；(v) a compound of the formula G _{2 ± a} P _{2 ± b} , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

   (vi)化学通式为Ge_3±aP_1±b的化合物，其中0<a≤0.2，且0<b≤0.2；(vi) a compound of the general formula Ge _3±a P _1±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

   (vii)化学通式为Ge_2±aP_3±b的化合物，其中0<a≤0.2，且0<b≤0.2；(vii) a compound of the formula G _{2 ± a} P _{3 ± b} , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

   (viii)化学通式为Ge_1±aP_5±b的化合物，其中0<a≤0.2，且0<b≤0.2； (viii) a compound of the general formula Ge _1±a P _5±b , wherein 0 < a ≤ 0.2, and 0 < b ≤ 0.2;

   (ix)化学通式为Ge_3±aP_4±b的化合物，其中0<a≤0.2，且0<b≤0.2。(ix) A compound having the chemical formula of Ge _3±a P _4±b , wherein 0 < a ≤ 0.2 and 0 < b ≤ 0.2.
4. 如权利要求1所述的一种锂离子/钠离子电池用负极活性材料，其中，所述由P和Ge所形成的二元非整比化合物包括由P和Ge所形成的整比化合物与过量的单质P和/或单质Ge所形成的固溶体的一种或多种。The negative electrode active material for a lithium ion/sodium ion battery according to claim 1, wherein the binary non-ratio compound formed of P and Ge comprises a compound and an excess amount formed by P and Ge. One or more of solid solutions formed by elemental P and/or elemental Ge.
5. 如权利要求1所述的一种锂离子/钠离子电池用负极活性材料，其中所述第二/第三复合物中，所述导电组元的质量为所述第二复合物总质量的10％～70％。The negative electrode active material for a lithium ion/sodium ion battery according to claim 1, wherein a mass of the conductive component in the second/third composite is 10 of a total mass of the second composite %~70%.
6. 如权利要求1所述的一种锂离子/钠离子电池用负极活性材料，其中所述第二/第三复合物中，所述导电组元的质量为所述第二复合物总质量的20％～60％。The negative electrode active material for a lithium ion/sodium ion battery according to claim 1, wherein a mass of the conductive component in the second/third composite is 20 of a total mass of the second composite. %~60%.
7. 如权利要求1所述的一种锂离子/钠离子电池用负极活性材料，其中所述导电组元包括具有导电能力的活性炭、天然石墨、石墨烯、石墨片、人造石墨、碳气凝胶、碳纤维、碳纳米管、石墨氧化物、还原石墨烯、炭黑、乙炔黑、金属Ni、金属Cu、化合物RuO₂、化合物TiC、聚苯胺、聚噻吩以及聚吡咯中的一种或者多种。The negative electrode active material for a lithium ion/sodium ion battery according to claim 1, wherein the conductive component comprises activated carbon having an electrical conductivity, natural graphite, graphene, graphite flakes, artificial graphite, carbon aerogel, One or more of carbon fiber, carbon nanotube, graphite oxide, reduced graphene, carbon black, acetylene black, metal Ni, metal Cu, compound RuO ₂ , compound TiC, polyaniline, polythiophene, and polypyrrole.
8. 一种锂离子/钠离子电池用负极，所述负极包含：A negative electrode for a lithium ion/sodium ion battery, the negative electrode comprising:

   集电器；和Current collector; and

   负极活性材料层，所述负极活性材料层形成在所述集电器的至少一个表面上并包含负极活性材料，a negative active material layer formed on at least one surface of the current collector and containing a negative active material,

   其中所述负极活性材料为权利要求1～7中任一项所限定的负极活性材料。The negative electrode active material is the negative electrode active material defined in any one of claims 1 to 7.
9. 一种锂离子电池，其包含：A lithium ion battery comprising:

   正极；positive electrode;

   负极；和Negative electrode; and

   设置在所述正极和所述负极之间的隔膜，a separator disposed between the positive electrode and the negative electrode,

   其中所述负极为权利要求8中所限定的负极。 Wherein the negative electrode is the negative electrode as defined in claim 8.
10. 一种钠离子电池，其包含：A sodium ion battery comprising:

    正极；positive electrode;

    负极；和Negative electrode; and

    设置在所述正极和所述负极之间的隔膜，a separator disposed between the positive electrode and the negative electrode,

    其中所述负极为权利要求8中所限定的负极。 Wherein the negative electrode is the negative electrode as defined in claim 8.

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