WO2022062320A1 - 一种含有金属元素梯度掺杂的负极材料及其应用 - Google Patents

一种含有金属元素梯度掺杂的负极材料及其应用 Download PDF

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WO2022062320A1
WO2022062320A1 PCT/CN2021/078604 CN2021078604W WO2022062320A1 WO 2022062320 A1 WO2022062320 A1 WO 2022062320A1 CN 2021078604 W CN2021078604 W CN 2021078604W WO 2022062320 A1 WO2022062320 A1 WO 2022062320A1
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negative electrode
electrode material
silicon oxide
metal element
gradient
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French (fr)
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殷营营
刘柏男
罗飞
李泓
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Tianmulake Excellent Anode Materials Co Ltd
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Tianmulake Excellent Anode Materials Co Ltd
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Priority to US18/246,727 priority Critical patent/US20230369572A1/en
Priority to EP21870709.9A priority patent/EP4220762A4/en
Publication of WO2022062320A1 publication Critical patent/WO2022062320A1/zh
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Definitions

  • the invention relates to the technical field of secondary battery materials, in particular to a negative electrode material containing gradient doping of metal elements and its application.
  • the demand for the performance of secondary batteries is increasing.
  • the development of positive and negative active materials with higher capacity has become the main focus of research and development.
  • the main commercially developed anode material with high energy density is silicon-based anode.
  • the silicon anode theoretically exhibits an ultra-high capacity of 4200 mAh/g, but it is accompanied by a volume expansion of about 300% during the lithium deintercalation process, which brings huge problems to its practical application.
  • Silica oxide (SiOx) has a smaller capacity than silicon, but has obvious advantages in relieving volume expansion and improving the cycle life of batteries.
  • the embodiments of the present invention provide a negative electrode material containing gradient doping of metal elements and applications thereof.
  • the negative electrode material has a metal element M doped with a concentration gradient, which can improve the cycle performance of silicon oxide; and the concentration gradually increases from the inside to the outside.
  • the gradient doping of SiO2 provides space for the expansion of SiO2 particles to slowly release the pressure, slows down the accumulation of stress, helps to alleviate the negative effects of volume expansion, and improves the cycle performance of the material.
  • an embodiment of the present invention provides a negative electrode material containing metal element gradient doping, the negative electrode material comprising a granular silicon oxide/M composite material with metal element M gradient doping;
  • the general formula of the silicon oxide is SiOx, wherein 0 ⁇ x ⁇ 2;
  • the metal element M includes one or more of Na, Mg, Al, Li, Mn, Fe, Co, Ni, Cu or Zn; in the negative electrode material, the content of the metal element M gradually decreases from the surface to the core , a doping profile with a continuous concentration gradient;
  • the general chemical formula of the silicon oxide/M composite material is SiM y O z , wherein 0 ⁇ y ⁇ 10, 0 ⁇ z ⁇ 10.
  • the average doping mass of the metal element M in the negative electrode material accounts for 5%-40% of the total mass of the negative electrode material
  • the content of the metal element M decreases in a continuous concentration gradient from 30%-50% of the surface to 0-20% of the core.
  • the doped region of the metal element M is a region that occupies from the inside to the outside the radius of the anode material particle [0-20%] to 100%.
  • the average particle size (D 50 ) of the negative electrode material is 0.1-40 ⁇ m; the particle specific surface area of the negative electrode material is 1 m 2 /g-40 m 2 /g.
  • the negative electrode material further comprises: a carbonaceous coating layer coated on the outer surface of the silicon oxide/M composite particles.
  • an embodiment of the present invention provides a negative electrode sheet, including the negative electrode material described in the first aspect above.
  • an embodiment of the present invention provides a lithium battery, including the negative electrode material described in the first aspect above.
  • the negative electrode material containing gradient doping of metal elements is a composite material particle containing a silicon oxide main body and a metal doping element M, the content of M gradually decreases from the particle surface to the inner core, and presents a continuous concentration gradient doping distribution.
  • This concentration gradient doping method can improve the cycling performance of SiO.
  • Silica particles undergo volume expansion during lithium intercalation.
  • the outer layer of the particle must also withstand the extrusion caused by the internal volume expansion of the particle.
  • the outer layer of the particle bears a more severe volume than the inner layer. deformation.
  • the compound formed by the doped metal element M and silicon oxide can play a role in relieving the volume expansion.
  • the gradient doping method with the M doping concentration gradually increasing from the inside to the outside can provide slow expansion of the silicon oxide particles. The space to release the pressure, slow down the accumulation of stress, help alleviate the negative effect of volume expansion, and improve the cycle performance of the material.
  • Fig. 1 is the distribution curve test chart of the Zn element content along the cross-sectional diameter of the negative electrode material containing metal element gradient doping provided by the embodiment of the present invention
  • FIG. 2 is a scanning electron microscope (SEM) image of a negative electrode material containing metal element gradient doping provided in an embodiment of the present invention.
  • the negative electrode material containing metal element gradient doping of the present invention includes a granular silicon oxide/M composite material with metal element M gradient doping.
  • the general formula of silicon oxide is SiOx, wherein 0 ⁇ x ⁇ 2; metal element M includes one or more of Na, Mg, Al, Li, Mn, Fe, Co, Ni, Cu or Zn; negative electrode In the material, the content of metal element M gradually decreases from the surface to the core, showing a continuous concentration gradient of doping distribution;
  • the general chemical formula of the silicon oxide/M composite is SiM y O z , where 0 ⁇ y ⁇ 10, 0 ⁇ z ⁇ 10.
  • the average particle diameter (D 50 ) of the negative electrode material of the present invention is 0.1-40 ⁇ m; the particle specific surface area of the negative electrode material is 1 m 2 /g-40 m 2 /g.
  • the negative electrode material may also include a carbonaceous coating layer coated on the outer surfaces of the silicon oxide/M composite particles.
  • the average doping mass of the metal element M in the negative electrode material accounts for 5%-40% of the total mass of the negative electrode material.
  • the content of metal element M decreases in a continuous concentration gradient from 30%-50% of the surface to 0-20% of the core.
  • the doped region of the metal element M is the region that occupies the radius of the anode material particle from the inside to the outside [0-20%] to 100%. , 5%, 10%, 15% or 20% of the area is undoped.
  • the doping amount of the metal element M in the core may or may not be zero, and there may be a region at the core that is not doped with the metal element M.
  • energy dispersive spectroscopy is linearly swept along the diameter direction of the particle section, and the M content curve obtained from the obtained EDS energy spectrum shows the specific surface M content from one end surface through the core to the other end through the curve. It gradually decreases first and then gradually increases, wherein in some instances there is a plateau region between the decreasing and increasing segments of the curve with a M content of zero, and in other instances there is no plateau region.
  • the negative electrode material proposed in this embodiment can be used in negative electrode plates and lithium-ion batteries, such as liquid lithium-ion batteries, semi-solid lithium-ion batteries, all-solid-state ion batteries or lithium-sulfur batteries, and can also be used in combination with other materials in practical applications. used as negative electrode material.
  • lithium-ion batteries such as liquid lithium-ion batteries, semi-solid lithium-ion batteries, all-solid-state ion batteries or lithium-sulfur batteries, and can also be used in combination with other materials in practical applications. used as negative electrode material.
  • the negative electrode material containing gradient doping of metal elements is a composite material particle containing a silicon oxide main body and a metal doping element M, the content of M gradually decreases from the particle surface to the inner core, and presents a continuous concentration gradient doping distribution.
  • This concentration gradient doping method can improve the cycling performance of SiO.
  • Silica particles undergo volume expansion during lithium intercalation.
  • the outer layer of the particle must also withstand the extrusion caused by the internal volume expansion of the particle.
  • the outer layer of the particle bears a more severe volume than the inner layer. deformation.
  • the compound formed by the doped metal element M and silicon oxide can play a role in relieving the volume expansion.
  • the gradient doping method with the M doping concentration gradually increasing from the inside to the outside can provide slow expansion of the silicon oxide particles.
  • the material structure using gradient doping of the present invention has more excellent effect of alleviating volume expansion and better cycle performance than conventional uniformly doped materials.
  • the preparation process and testing process are as follows:
  • the dried precursor is placed in a high-temperature furnace, sintered at 1200° C. for 3 hours under a nitrogen atmosphere, and subjected to natural cooling, pulverization, and sieving to obtain a Zn gradient doped silicon oxide composite material;
  • the doping reaction used in the present invention is a solid-solid reaction.
  • the doping source first adheres to the surface of the silicon oxide particles, and then undergoes high-temperature treatment.
  • the doping elements are gradually diffused into the silicon oxide particles driven by their own concentration differences.
  • the doping diffusion process is closely related to the doping process.
  • the concentration gradient of the impurity source, the diffusion time, the diffusion temperature, the size of the particle size of the silicon oxide itself, the strength of the adhesion of the dopant source, and the size of the particle size of the dopant source have a very important relationship.
  • the main factors of impurity concentration distribution, through the control of these variables, different distributions of Zn can be obtained.
  • FIG. 2 The scanning electron microscope (SEM) image of the prepared Zn concentration gradient doped silicon oxide particles is shown in FIG. 2 , which is irregular potato-like at the micron level.
  • the prepared silicon oxide composite material, carbon black (SP) and sodium carboxymethyl cellulose (CMC) are prepared in a ratio of 7:2:1 to prepare a negative electrode slurry, which is coated and dried to make a negative electrode pole piece.
  • metal Li as the counter electrode, a button battery was assembled in a glove box, and the charge-discharge test was carried out. The battery test results are listed in Table 1.
  • This embodiment provides a negative electrode material with Zn gradient doping.
  • the preparation process and testing process are as follows:
  • the prepared silicon oxide composite material, carbon black (SP) and sodium carboxymethyl cellulose (CMC) are prepared in a ratio of 7:2:1 to prepare a negative electrode slurry, which is coated and dried to make a negative electrode pole piece.
  • a negative electrode slurry which is coated and dried to make a negative electrode pole piece.
  • nickel cobalt manganate lithium NCM 811 was assembled in the glove box, and the charge and discharge test was carried out.
  • the battery test results are listed in Table 1.
  • This embodiment provides a negative electrode material with Zn gradient doping.
  • the preparation process and testing process are as follows:
  • This embodiment provides a negative electrode material with Ni gradient doping.
  • the preparation process and testing process are as follows:
  • the prepared silicon oxide composite material, carbon black (SP), and sodium carboxymethyl cellulose (CMC) are prepared in a ratio of 7:2:1 to prepare a negative electrode slurry, which is coated and dried to prepare a negative electrode. piece.
  • the ternary cathode material nickel cobalt manganese lithium NCM 333 was assembled into a button battery in a glove box, and the charge and discharge test was carried out. The battery test results are listed in Table 1.
  • This embodiment provides a negative electrode material with Ni gradient doping.
  • the preparation process and testing process are as follows:
  • the prepared silicon oxide composite material, carbon black (SP), and sodium carboxymethyl cellulose (CMC) are prepared in a ratio of 7:2:1 to prepare a negative electrode slurry, which is coated and dried to prepare a negative electrode. piece.
  • the ternary cathode material nickel cobalt manganate lithium NCM 523 was assembled into a button battery in a glove box, and the charge and discharge test was carried out. The battery test results are listed in Table 1.
  • This embodiment provides a negative electrode material with Ni gradient doping.
  • the preparation process and testing process are as follows:
  • the prepared silicon oxide composite material, carbon black (SP), and sodium carboxymethyl cellulose (CMC) are prepared in a ratio of 7:2:1 to prepare a negative electrode slurry, which is coated and dried to prepare a negative electrode. piece.
  • a button battery was assembled in a glove box with the ternary positive material nickel-cobalt-aluminate NCA as the counter electrode, and the charge-discharge test was carried out. The battery test results are listed in Table 1.
  • This embodiment provides a negative electrode material with Al gradient doping.
  • the preparation process and testing process are as follows:
  • This embodiment provides a negative electrode material with Na gradient doping.
  • the preparation process and testing process are as follows:
  • This embodiment provides a negative electrode material with Al gradient doping.
  • the preparation process and testing process are as follows:
  • the prepared silicon oxide composite material, carbon black (SP), and sodium carboxymethyl cellulose (CMC) are prepared in a ratio of 7:2:1 to prepare a negative electrode slurry, which is coated and dried to prepare a negative electrode. piece.
  • metal Li as the counter electrode, a button battery was assembled in a glove box, and the charge-discharge test was carried out. The battery test results are listed in Table 1.
  • This embodiment provides a negative electrode material with Mg gradient doping.
  • the preparation process and testing process are as follows:
  • the prepared silicon oxide composite material, carbon black (SP), and sodium carboxymethyl cellulose (CMC) are prepared in a ratio of 7:2:1 to prepare a negative electrode slurry, which is coated and dried to make a negative electrode pole piece.
  • the ternary cathode material NCM 811 was assembled into a button battery in a glove box, and the charge-discharge test was carried out. The battery test results are listed in Table 1.
  • This embodiment provides a negative electrode material with Fe gradient doping.
  • the preparation process and testing process are as follows:
  • This embodiment provides a negative electrode material with Co gradient doping.
  • the preparation process and testing process are as follows:
  • the prepared silicon oxide composite material, carbon black (SP), and sodium carboxymethyl cellulose (CMC) are prepared in a ratio of 7:2:1 to prepare a negative electrode slurry, which is coated and dried to make a negative electrode pole piece.
  • metal Li as the counter electrode
  • polyolefin-based gel polymer electrolyte membrane as the semi-solid electrolyte
  • This embodiment provides a negative electrode material with Co gradient doping.
  • the preparation process and testing process are as follows:
  • This embodiment provides a negative electrode material with Li gradient doping.
  • the preparation process and testing process are as follows:
  • This embodiment provides a negative electrode material with Cu gradient doping.
  • the preparation process and testing process are as follows:
  • This embodiment provides a negative electrode material with Mn gradient doping.
  • the preparation process and testing process are as follows:
  • the present comparative example provides a negative electrode material with uniform doping of Zn.
  • the preparation process and testing process are as follows:
  • Example 1 has the material cycle performance of the concentration gradient doping method (50 cycle capacity retention rate). ) is significantly better.
  • silicon oxide is intercalated with lithium, the entire particle expands.
  • the outer shell of the particle also bears the extrusion from the expansion of the internal particle, which bears a greater stress than the internal position.
  • the gradient doping method with high outer and inner low can better adapt to the gradually increasing stress of the particles from the inside to the outside, and has a significant effect on slowing down the volume expansion, so as to achieve the advantage of improving the cycle performance.

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Abstract

一种含有金属元素梯度掺杂的负极材料及其应用，其中，负极材料包括具有金属元素M梯度掺杂的颗粒状氧化亚硅/M复合材料；所述氧化亚硅的通式为SiO x，其中0<x<2；所述金属元素M包括Na、Mg、Al、Li、Mn、Fe、Co、Ni、Cu或Zn中的一种或几种；所述负极材料中，金属元素M的含量从表面到核心逐渐减少，呈连续浓度梯度的掺杂分布；所述氧化亚硅/M复合材料的化学通式为SiM yO z，其中0<y<10，0<z<10。

Description

一种含有金属元素梯度掺杂的负极材料及其应用
本申请要求于2020年09月27日提交中国专利局、申请号为202011031911.2、发明名称为“一种含有金属元素梯度掺杂的负极材料及其应用”的中国专利申请的优先权。
技术领域
本发明涉及二次电池材料技术领域，尤其涉及一种含有金属元素梯度掺杂的负极材料及其应用。
背景技术
随着锂离子电池在动力领域的应用，人们对二次电池性能的需求日益增加。为了提高能量密度，开发更高容量的正极、负极活性材料成为了主要集中的研发方向。目前商业上主要研发的高能量密度的负极材料为硅基负极。硅负极理论上表现出4200mAh/g的超高容量，但是在脱嵌锂过程中，伴随着约300％的体积膨胀，为其实际应用带来了巨大的问题。氧化亚硅(SiOx)相比硅单质容量小，但是对于缓解体积膨胀提高电池的循环寿命有着明显的优势。不过，氧化亚硅在首周嵌锂时，锂与二氧化硅反应会生成不可逆的锂氧化物，导致锂的损失，首圈充放电效率下降到75％以下。另外，虽然相比于硅的体积膨胀小，但是氧化亚硅也存在较为明显的体积膨胀。
为了提高氧化亚硅的首效，减缓体积膨胀，目前常用预理化或掺杂其他元素的方式对其进行改进。但具体的预锂化、掺杂方式的实施和所用材料的选择，带来的改进效果也是不同的。到目前为止，循环性能差仍是制 约氧化亚硅产业化的主要原因。提高氧化亚硅的首效，缓解脱嵌锂前后的体积膨胀是目前主要攻克的方向。
发明内容
本发明实施例提供了一种含有金属元素梯度掺杂的负极材料及其应用，负极材料具有浓度梯度掺杂的金属元素M，能够提高氧化亚硅的循环性能；而从内到外浓度逐渐增加的梯度掺杂，为氧化亚硅颗粒的膨胀提供缓慢释放压力的空间，减缓应力的积累，有助于缓解体积膨胀带来的消极影响，提高材料的循环性能。
第一方面，本发明实施例提供了一种含有金属元素梯度掺杂的负极材料，所述负极材料包括具有金属元素M梯度掺杂的颗粒状氧化亚硅/M复合材料；
所述氧化亚硅的通式为SiOx，其中0<x<2；
所述金属元素M包括Na、Mg、Al、Li、Mn、Fe、Co、Ni、Cu或Zn中的一种或几种；所述负极材料中，金属元素M的含量从表面到核心逐渐减少，呈连续浓度梯度的掺杂分布；
所述氧化亚硅/M复合材料的化学通式为SiM yO z，其中0<y<10，0<z<10。
优选的，所述金属元素M在负极材料中的平均掺杂质量占所述负极材料总质量的5％-40％；
其中，所述金属元素M的含量从表面的30％-50％到核心的0-20％呈连续浓度梯度递减。
进一步优选的，所述金属元素M的掺杂区域为由内向外占据负极材料颗粒半径[0-20％]至100％的区域。
优选的，所述负极材料的颗粒平均粒径(D 50)为0.1-40μm；所述负极材料的颗粒比表面积为1m 2/g-40m 2/g。
优选的，所述负极材料还包括：包覆在氧化亚硅/M复合材料颗粒外表 面的碳质包覆层。
第二方面，本发明实施例提供了一种负极片，包括上述第一方面所述的负极材料。
第三方面，本发明实施例提供了一种锂电池，包括上述第一方面所述的负极材料。
本发明实施例提供的含有金属元素梯度掺杂的负极材料，为包含氧化亚硅主体及金属掺杂元素M的复合材料颗粒，M的含量从颗粒表面到内核逐渐减小，并呈现连续浓度梯度的掺杂分布。这种浓度梯度掺杂的方式能够提高氧化亚硅的循环性能。氧化亚硅颗粒在嵌锂时发生体积膨胀，颗粒外层除了承受自身体积膨胀带来的应力外，还要承受颗粒内部体积膨胀带来的挤压，颗粒外层要比内层承受更加剧烈的体积形变。掺杂的金属元素M与氧化亚硅形成的复合物可以起到缓解体积膨胀的作用，从内到外M掺杂浓度逐渐增加的梯度掺杂的方式，可为氧化亚硅颗粒的膨胀提供缓慢释放压力的空间，减缓应力的积累，有助于缓解体积膨胀带来的消极影响，以提高材料的循环性能。
附图说明
下面通过附图和实施例，对本发明实施例的技术方案做进一步详细描述。
图1为本发明实施例提供的含有金属元素梯度掺杂的负极材料沿剖面直径的Zn元素含量的分布曲线测试图；
图2为本发明实施例提供的含有金属元素梯度掺杂的负极材料的扫描电子显微镜(SEM)图。
具体实施方式
下面通过附图和具体的实施例，对本发明进行进一步的说明，但应当理解为这些实施例仅仅是用于更详细说明之用，而不应理解为用以任何形 式限制本发明，即并不意于限制本发明的保护范围。
本发明的含有金属元素梯度掺杂的负极材料，包括具有金属元素M梯度掺杂的颗粒状氧化亚硅/M复合材料。
其中，氧化亚硅的通式为SiOx，其中0<x<2；金属元素M包括Na、Mg、Al、Li、Mn、Fe、Co、Ni、Cu或Zn中的一种或几种；负极材料中，金属元素M的含量从表面到核心逐渐减少，呈连续浓度梯度的掺杂分布；
氧化亚硅/M复合材料的化学通式为SiM yO z，其中0<y<10，0<z<10。
本发明负极材料的颗粒平均粒径(D 50)为0.1-40μm；负极材料的颗粒比表面积为1m 2/g-40m 2/g。
负极材料还可以包括包覆在氧化亚硅/M复合材料颗粒外表面的碳质包覆层。
进一步的，金属元素M在负极材料中的平均掺杂质量占所述负极材料总质量的5％-40％。金属元素M的含量从表面的30％-50％到核心的0-20％呈连续浓度梯度递减。在本发明中，金属元素M的掺杂区域为由内向外占据负极材料颗粒半径[0-20％]至100％的区域，比如可以是负极材料全部掺杂，或者负极材料核心内有2％、5％、10％、15％或20％的区域无掺杂。以上表明，金属元素M在核心的掺杂量可以为零也可以不为零，核心处可以存在不含金属元素M掺杂的区域。
在不同的实施例中，沿颗粒切面的直径方向线扫能量色散光谱(EDS)，从获得的EDS能谱可得到的M含量曲线，通过曲线呈现由一端表面经核心至另一端比表面M含量先逐渐减小后逐渐增加，其中在一些实例中曲线的减小和增加段之间存在平台区M含量为零，在另一些实例中不存在平台区。
本实施例提出的负极材料可以用于负极极片以及锂离子电池中，如液态锂离子电池、半固态锂离子电池、全固态离子电池或锂硫电池，在实际应用中还可以与其他材料共同使用作为负极材料。
本发明实施例提供的含有金属元素梯度掺杂的负极材料，为包含氧化 亚硅主体及金属掺杂元素M的复合材料颗粒，M的含量从颗粒表面到内核逐渐减小，并呈现连续浓度梯度的掺杂分布。这种浓度梯度掺杂的方式能够提高氧化亚硅的循环性能。氧化亚硅颗粒在嵌锂时发生体积膨胀，颗粒外层除了承受自身体积膨胀带来的应力外，还要承受颗粒内部体积膨胀带来的挤压，颗粒外层要比内层承受更加剧烈的体积形变。掺杂的金属元素M与氧化亚硅形成的复合物可以起到缓解体积膨胀的作用，从内到外M掺杂浓度逐渐增加的梯度掺杂的方式，可为氧化亚硅颗粒的膨胀提供缓慢释放压力的空间，减缓应力的积累，有助于缓解体积膨胀带来的消极影响，以提高材料的循环性能。本发明这种采用梯度掺杂的材料结构，比常规均匀掺杂的材料具有更优异的缓解体积膨胀的效果和更好的循环性能。
为更好的理解本发明提供的技术方案，下述以多个具体实例分别说明采用含有不同金属元素梯度掺杂的负极材料，及应用于锂离子电池的方法和电池特性。
实施例1
本实施例提供了一种具有Zn梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L的醋酸锌溶液、2mol/L的氢氧化钠溶液和2mol/L的氨水。
(2)将氧化亚硅颗粒与去离子水按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入醋酸锌溶液，其中引入锌元素的质量与氧化亚硅的质量比为1：3，待混合均匀后，将氢氧化钠溶液与氨水一同加入到反应容器中，调节pH至11，并持续搅拌10小时。整个过程中的反应温度为60℃。
(3)将沉淀的浆料多次洗涤离心，于80℃烘箱中烘12小时。
(4)将烘干的前驱体至于高温炉中，在氮气气氛下1200℃烧结3小 时，经自然冷却、粉碎、筛分，得到Zn梯度掺杂的氧化亚硅复合材料；
(5)将筛分后的样品与石油沥青按照20:1的质量比混合均匀，至于高温炉中，在氮气氛围下经900℃热处理2小时，即制备出具有碳层包覆的Zn浓度梯度掺杂的氧化亚硅复合负极。
(6)将制备的Zn浓度梯度掺杂的氧化亚硅颗粒利用聚焦离子束切开，在扫描电镜下做能谱分析。沿着颗粒剖面直径，Zn元素的含量分布曲线如图1所示。
因为本发明所采用的掺杂反应是固固反应。在浆料状态时，掺杂源首先粘附在氧化亚硅颗粒表面，之后进行高温处理，掺杂元素在自身浓度差的驱使下，逐步扩散到氧化亚硅颗粒内部，掺杂扩散过程与掺杂源的浓度梯度、扩散的时间、扩散的温度、氧化亚硅自身粒径的大小、掺杂源粘附的强度、掺杂源粒径的大小等因素有着非常重要的关系，是影响最终掺杂浓度分布的主要因素，通过这些变量的控制，可得到Zn的不同分布。
(7)制备的Zn浓度梯度掺杂的氧化亚硅颗粒的扫描电子显微镜(SEM)图如图2所示，为微米级别的不规则土豆状。
(8)将制备的氧化亚硅复合材料与碳黑(SP)、羧甲基纤维素钠(CMC)按照7：2：1的比例制备负极浆料，经涂覆、烘干后制成负极极片。以金属Li作为对电极，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例2
本实施例提供了一种具有Zn梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L黃原酸锌的丙酮溶液。
(2)将氧化亚硅颗粒与丙酮按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入黃原酸锌的丙酮溶液，其中引入的锌元素质量与氧化亚硅的质量比为1：4，并持续搅拌10小时， 之后至于80℃烘箱中烘12小时；
(3)将烘干的前驱体至于高温炉中，在氮气气氛下1200℃烧结3小时，经自然冷却、粉碎、筛分，得到Zn梯度掺杂的氧化亚硅复合材料；
(4)将筛分后的样品与石油沥青按照20:1的质量比混合均匀，至于高温炉中，在氮气氛围下经900℃热处理2小时，即制备出具有碳层包覆的Zn浓度梯度掺杂的氧化亚硅复合负极。
(5)将制备的氧化亚硅复合材料与碳黑(SP)、羧甲基纤维素钠(CMC)按照7：2：1的比例制备负极浆料，经涂覆、烘干后制成负极极片。以三元正极材料镍钴锰酸锂NCM 811为对电极，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例3
本实施例提供了一种具有Zn梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L的醋酸锌溶液、2mol/L的氢氧化钠溶液和2mol/L的氨水。
(2)将氧化亚硅颗粒与去离子水按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入醋酸锌溶液，其中引入的锌元素质量与氧化亚硅的质量比为1：5，待混合均匀后，将氢氧化钠溶液与氨水一同加入到反应容器中，调节pH至11，并持续搅拌10小时。整个过程中的反应温度为60℃。
(3)将沉淀的浆料多次洗涤离心，于80℃烘箱中烘12小时。
(4)将烘干的前驱体至于高温炉中，在氮气气氛下1200℃烧结3小时，经自然冷却、粉碎、筛分，得到Zn梯度掺杂的氧化亚硅复合材料；
(5)将筛分后的样品与石油沥青按照20:1的质量比混合均匀，至于高温炉中，在氮气氛围下经900℃热处理2小时，即制备出具有碳层包覆的Zn浓度梯度掺杂的氧化亚硅复合负极。
(6)将制备的氧化亚硅复合材料与碳黑(SP)、羧甲基纤维素钠(CMC)按照7：2：1的比例制备负极浆料，经涂覆、烘干后制成负极极片。以正极材料钴酸锂(LCO)为对电极，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例4
本实施例提供了一种具有Ni梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L的氯化镍溶液、2mol/L的氢氧化钠溶液和2mol/L的氨水。
(2)将氧化亚硅颗粒与去离子水按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入氯化镍溶液，其中引入的镍元素质量与氧化亚硅的质量比为1：3，待混合均匀后，将氢氧化钠溶液与氨水一同加入到反应容器中，调节pH至11，并持续搅拌10小时。整个过程中的反应温度为60℃。
(3)将沉淀的浆料多次洗涤离心，于80℃烘箱中烘干12小时。
(4)将烘干的前驱体至于高温炉中，在氮气气氛下1200℃烧结3小时，经自然冷却、粉碎、筛分，得到Ni梯度掺杂的氧化亚硅复合材料；
(5)将筛分后的样品与石油沥青按照20:1的质量比例混合均匀，至于高温炉中，在氮气氛围下经900℃热处理2小时，制备出具有碳层包覆的Ni浓度梯度掺杂的氧化亚硅复合负极。
(6)将制备的氧化亚硅复合材料与碳黑(SP)、羧甲基纤维素钠(CMC)按照7：2：1的比例制备负极浆料，涂覆、烘干后制备成负极极片。三元正极材料镍钴锰酸锂NCM 333，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例5
本实施例提供了一种具有Ni梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L的硝酸镍溶液、2mol/L的氢氧化钠溶液和2mol/L的氨水。
(2)将氧化亚硅颗粒与去离子水按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入硝酸镍溶液，其中引入的镍元素质量与氧化亚硅的质量比为1：4，待混合均匀后，将氢氧化钠溶液与氨水一同加入到反应容器中，调节pH至11，并持续搅拌10小时。整个过程中的反应温度为60℃。
(3)将沉淀的浆料多次洗涤离心，于80℃烘箱中烘干12小时。
(4)将烘干的前驱体至于高温炉中，在氮气气氛下1200℃烧结3小时，经自然冷却、粉碎、筛分，得到Ni梯度掺杂的氧化亚硅复合材料；
(5)将筛分后的样品与石油沥青按照20:1的质量比例混合均匀，至于高温炉中，在氮气氛围下经900℃热处理2小时，制备出具有碳层包覆的Ni浓度梯度掺杂的氧化亚硅复合负极。
(6)将制备的氧化亚硅复合材料与碳黑(SP)、羧甲基纤维素钠(CMC)按照7：2：1的比例制备负极浆料，涂覆、烘干后制备成负极极片。三元正极材料镍钴锰酸锂NCM 523，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例6
本实施例提供了一种具有Ni梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L二茂镍的乙醚溶液。
(2)将氧化亚硅颗粒与乙醚按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入二茂镍的乙醚溶液，其中引入的镍元素质量与氧化亚硅的质量比为1：5，持续搅拌10小时。之后将浆料于80℃烘箱中烘干12小时。
(3)将烘干的前驱体至于高温炉中，在氮气气氛下1200℃烧结3小时，经自然冷却、粉碎、筛分，得到Ni梯度掺杂的氧化亚硅复合材料；
(4)将筛分后的样品与石油沥青按照20:1的质量比例混合均匀，至于高温炉中，在氮气氛围下经900℃热处理2小时，制备出具有碳层包覆的Ni浓度梯度掺杂的氧化亚硅复合负极。
(5)将制备的氧化亚硅复合材料与碳黑(SP)、羧甲基纤维素钠(CMC)按照7：2：1的比例制备负极浆料，涂覆、烘干后制备成负极极片。以三元正极材料镍钴铝酸锂NCA为对电极，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例7
本实施例提供了一种具有Al梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L的硫酸铝Al 2(SO 4) 3溶液、1mol/L的氨水。
(2)将氧化亚硅颗粒与去离子水按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入Al 2(SO 4) 3溶液，其中引入的Al元素质量与氧化亚硅的质量比为1：3，待混合均匀后，将氨水加入到反应容器中，调节pH至8，并持续搅拌10小时。整个过程中的反应温度为60℃。
(3)将沉淀的浆料多次洗涤离心，于80℃烘箱中烘干12小时。
(4)将烘干的前驱体至于高温炉中，在氮气气氛下1200℃烧结3小时，经自然冷却、粉碎、筛分，得到Al梯度掺杂的氧化亚硅复合材料；
(5)将筛分后的样品与石油沥青按照20:1的质量比例混合均匀，至于高温炉中，在氮气氛围下经900℃热处理2小时，即制备出具有碳层包覆的Al浓度梯度掺杂的氧化亚硅复合负极。
(6)将制备的氧化亚硅复合材料与碳黑(SP)、羧甲基纤维素钠(CMC)按照7：2：1的比例制备负极浆料，涂覆、烘干后制备成负极极片。以正 极材料磷酸铁锂(LFP)为对电极，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例8
本实施例提供了一种具有Na梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L的柠檬酸钠Na 3C 6H 5O 7·2H 2O溶液。
(2)将氧化亚硅颗粒与去离子水按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入Na 3C 6H 5O 7·2H 2O溶液，其中引入的Na元素质量与氧化亚硅的质量比为1：4，持续搅拌10小时，之后置于80℃烘箱中烘干12小时。
(3)将烘干的前驱体至于高温炉中，在氮气气氛下1200℃烧结3小时，经自然冷却、粉碎、筛分，得到Na梯度掺杂的氧化亚硅复合材料；
(4)将筛分后的样品与葡糖糖按照20:1的质量比例混合均匀，至于高温炉中，在氮气氛围下经900℃热处理2小时，即制备出具有碳层包覆的Na浓度梯度掺杂的氧化亚硅复合负极。
(4)将制备的氧化亚硅复合材料与碳黑(SP)、羧甲基纤维素钠(CMC)按照7：2：1的比例制备负极浆料，涂覆、烘干后制备成负极极片。以正极材料锰酸锂(LMO)为对电极，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例9
本实施例提供了一种具有Al梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L异丙醇铝的乙醇溶液。
(2)将氧化亚硅颗粒与乙醇按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加异丙醇铝的乙醇溶液，其中引入的Al元素质量与氧化亚硅的质量比为1：5，持续搅拌10小时，之 后置于80℃烘箱中烘干12小时。
(3)将烘干的前驱体至于高温炉中，在氮气气氛下1200℃烧结3小时，经自然冷却、粉碎、筛分，得到Al梯度掺杂的氧化亚硅复合材料；
(4)将筛分后的样品与石油沥青按照20:1的质量比例混合均匀，至于高温炉中，在氮气氛围下经900℃热处理2小时，即制备出具有碳层包覆的Al浓度梯度掺杂的氧化亚硅复合负极。
(5)将制备的氧化亚硅复合材料与碳黑(SP)、羧甲基纤维素钠(CMC)按照7：2：1的比例制备负极浆料，涂覆、烘干后制备成负极极片。以金属Li作为对电极，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例10
本实施例提供了一种具有Mg梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L的醋酸镁溶液、2mol/L的氢氧化钠溶液和2mol/L的氨水。
(2)将氧化亚硅颗粒与去离子水按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入醋酸镁溶液，其中引入镁元素的质量与氧化亚硅的质量比为1：3，待混合均匀后，将氢氧化钠溶液与氨水一同加入到反应容器中，调节pH至11，并持续搅拌10小时。整个过程中的反应温度为60℃。
(3)将沉淀的浆料多次洗涤离心，于80℃烘箱中烘12小时。
(4)将烘干的前驱体至于真空中，真空环境下1200℃烧结3小时，经自然冷却、粉碎、筛分，得到Mg梯度掺杂的氧化亚硅复合材料；
(5)将筛分后的样品置于回转炉中，在900℃下通体积比为3:1的氩气和乙炔混合气体，并保温2小时，即制备出具有碳层包覆的Mg浓度梯度掺杂的氧化亚硅复合负极。
(6)将制备的氧化亚硅复合材料与碳黑(SP)、羧甲基纤维素钠(CMC)按照7：2：1的比例制备负极浆料，经涂覆、烘干后制成负极极片。三元正极材料NCM 811，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例11
本实施例提供了一种具有Fe梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L的醋酸铁溶液、2mol/L的氢氧化钠溶液和2mol/L的氨水。
(2)将氧化亚硅颗粒与去离子水按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入醋酸铁溶液，其中引入的铁元素质量与氧化亚硅的质量比为1：3，待混合均匀后，将氢氧化钠溶液与氨水一同加入到反应容器中，调节pH至11，并持续搅拌10小时。整个过程中的反应温度为60℃。
(3)将沉淀的浆料多次洗涤离心，于80℃烘箱中烘12小时。
(4)将烘干的前驱体至于真空炉中，真空环境下1000℃烧结3小时，经自然冷却、粉碎、筛分，得到Fe梯度掺杂的氧化亚硅复合材料；
(5)将筛分后的样品置于回转炉中，在1000℃下通体积比为3:1的氩气和甲烷的混合气体，并保温2小时，即制备出具有碳层包覆的Fe浓度梯度掺杂的氧化亚硅复合负极。
(6)将制备的氧化亚硅复合材料与碳黑(SP)、羧甲基纤维素钠(CMC)按照7：2：1的比例制备负极浆料，经涂覆、烘干后制成负极极片。以金属Li作为对电极，以石榴石型Li 7La 3Zr 2O 12(LLZO)作为固态电解质，在手套箱中组装成全固态纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例12
本实施例提供了一种具有Co梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L的醋酸钴溶液、2mol/L的氢氧化钠溶液和2mol/L的氨水。
(2)将氧化亚硅颗粒与去离子水按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入醋酸钴溶液，其中引入的钴元素质量与氧化亚硅的质量比为1：3，待混合均匀后，将氢氧化钠溶液与氨水一同加入到反应容器中，调节pH至11，并持续搅拌10小时。整个过程中的反应温度为60℃。
(3)将沉淀的浆料多次洗涤离心，于80℃烘箱中烘12小时。
(4)将烘干的前驱体至于高温炉中，氩气气氛下1000℃烧结3小时，经自然冷却、粉碎、筛分，得到Co梯度掺杂的氧化亚硅复合材料；
(5)将筛分后的样品置于回转炉中，在1000℃下通体积比为3:1的氩气和甲烷的混合气体，并保温2小时，即制备出具有碳层包覆的Co浓度梯度掺杂的氧化亚硅复合负极。
(6)将制备的氧化亚硅复合材料与碳黑(SP)、羧甲基纤维素钠(CMC)按照7：2：1的比例制备负极浆料，经涂覆、烘干后制成负极极片。以金属Li作为对电极，以聚烯烃基凝胶聚合物电解质膜作为半固态电解质，在手套箱中组装成半固态纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例13
本实施例提供了一种具有Co梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L的硝酸钴溶液、2mol/L的氢氧化钠溶液和2mol/L的氨水。
(2)将氧化亚硅颗粒与去离子水按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入硝酸钴溶液，其中引入的钴元素质量与氧化亚硅的质量比为1：3，待混合均匀后，将氢氧化 钠溶液与氨水一同加入到反应容器中，调节pH至11，并持续搅拌10小时。整个过程中的反应温度为60℃。
(3)将沉淀的浆料多次洗涤离心，于80℃烘箱中烘12小时。
(4)将烘干的前驱体至于高温炉中，氩气气氛下1000℃烧结3小时，经自然冷却、粉碎、筛分，得到Co梯度掺杂的氧化亚硅复合材料；
(5)将筛分后的样品置于回转炉中，在1000℃下通体积比为3:1的氩气和甲烷的混合气体，并保温2小时，即制备出具有碳层包覆的Co浓度梯度掺杂的氧化亚硅复合负极。
(6)将制备的氧化亚硅复合材料与商品石墨按比例复合为450mAh/g的复合材料，与正极材料钴酸锂(LCO)为对电极，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例14
本实施例提供了一种具有Li梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L碳酸锂溶液，用稀盐酸调节pH至3。
(2)将氧化亚硅颗粒与去离子水按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入碳酸锂溶液，其中引入的Li元素质量与氧化亚硅的质量比为1：5，持续搅拌10小时，之后置于80℃烘箱中烘干12小时。
(3)将烘干的前驱体至于高温炉中，在氮气气氛下1200℃烧结3小时，经自然冷却、粉碎、筛分，得到Li梯度掺杂的氧化亚硅复合材料；
(4)将筛分后的样品与石油沥青按照20:1的质量比例混合均匀，至于高温炉中，在氮气氛围下经900℃热处理2小时，即制备出具有碳层包覆的Li浓度梯度掺杂的氧化亚硅复合负极。
(6)将制备的氧化亚硅复合材料与商品石墨按比例复合为550mAh/g的复合材料,以金属Li作为对电极，在手套箱中组装成纽扣电池，进行充 放电测试，电池测试结果列于表1。
实施例15
本实施例提供了一种具有Cu梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L的硫酸铜CuSO 4溶液、1mol/L的氨水。
(2)将氧化亚硅颗粒与去离子水按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入CuSO 4溶液，其中引入的Cu元素质量与氧化亚硅的质量比为1：5，待混合均匀后，将氨水加入到反应容器中，调节pH至8，并持续搅拌10小时。整个过程中的反应温度为60℃。
(3)将沉淀的浆料多次洗涤离心，于80℃烘箱中烘干12小时。
(4)将烘干的前驱体至于高温炉中，在氮气气氛下1200℃烧结3小时，经自然冷却、粉碎、筛分，得到Cu梯度掺杂的氧化亚硅复合材料；
(5)将筛分后的样品与石油沥青按照20:1的质量比例混合均匀，至于高温炉中，在氮气氛围下经900℃热处理2小时，即制备出具有碳层包覆的Cu浓度梯度掺杂的氧化亚硅复合负极。
(6)将制备的氧化亚硅复合材料与商品石墨按比例复合为550mAh/g的复合材料,以金属Li作为对电极，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
实施例16
本实施例提供了一种具有Mn梯度掺杂的负极材料。
制备过程和测试过程如下：
(1)首先配置1mol/L的醋酸锰Mn(CH 3COO) 2溶液、1mol/L的氨水。
(2)将氧化亚硅颗粒与去离子水按照1：10的比例经过充分搅拌后混合均匀，制备成氧化亚硅的浆料。之后边搅拌边加入Mn(CH 3COO) 2溶液，其中引入的Mn元素质量与氧化亚硅的质量比为1：5，待混合均匀后，将 氨水加入到反应容器中，调节pH至8，并持续搅拌10小时。整个过程中的反应温度为60℃。
(3)将沉淀的浆料多次洗涤离心，于80℃烘箱中烘干12小时。
(4)将烘干的前驱体至于高温炉中，在氮气气氛下1200℃烧结3小时，经自然冷却、粉碎、筛分，得到Mn梯度掺杂的氧化亚硅复合材料；
(5)将筛分后的样品与石油沥青按照20:1的质量比例混合均匀，至于高温炉中，在氮气氛围下经900℃热处理2小时，即制备出具有碳层包覆的Mn浓度梯度掺杂的氧化亚硅复合负极。
(6)将制备的氧化亚硅复合材料与商品石墨按比例复合为550mAh/g的复合材料,以金属Li作为对电极，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
对比例1
本对比例提供了一种具有Zn均匀掺杂的负极材料。
制备过程和测试过程如下：
(1)将金属Zn与氧化亚硅按照1:3的比例混合均匀，至于真空反应炉的坩埚中。抽真空至10Pa后,逐步升温至1200℃，并保温3小时。真空高温环境下金属Zn与氧化亚硅先后挥发为锌蒸汽与氧化亚硅蒸汽，两种蒸汽在真空反应炉内的冷却板相遇并沉积。出料后经过粉碎、筛分，得到Zn均匀掺杂的氧化亚硅复合材料。
(2)将筛分后的样品与石油沥青按照20:1的质量比混合均匀，至于高温炉中，在氮气氛围下经900℃热处理2小时，即制备出具有碳层包覆的Zn均匀掺杂的氧化亚硅复合负极。
(3)将制备的氧化亚硅复合材料与碳黑(SP)、羧甲基纤维素钠(CMC)按照7：2：1的比例制备负极浆料，涂覆、烘干后制备成负极极片。以金属Li作为对电极，在手套箱中组装成纽扣电池，进行充放电测试，电池测试结果列于表1。
Figure PCTCN2021078604-appb-000001
表1
如表1所示，本发明上述各实施例中浓度梯度掺杂的颗粒，随着掺杂量的增加，氧化亚硅的克容量有所减小，但是首圈效率尤其是循环性能有明显的提高。对比实施例1和对比例1，同样总掺杂量下，二者首周克容量和首周效率差别不大，但是实施例1具有浓度梯度掺杂方式的材料循环性能(50周容量保持率)明显更好。氧化亚硅嵌锂时，整个颗粒发生膨胀，颗粒外壳处除了承受自身膨胀应力外，还要承受来自内部颗粒膨胀带来的挤压，比内部位置承受更大的应力。外高内低的梯度掺杂方式更能适应这种颗粒由内到外逐渐累积增大的应力，对于减缓体积膨胀有明显作用，以达到提高循环性能的优势。
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而 已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (8)

  1. 一种含有金属元素梯度掺杂的负极材料，其特征在于，所述负极材料包括具有金属元素M梯度掺杂的颗粒状氧化亚硅/M复合材料；
    所述氧化亚硅的通式为SiOx，其中0<x<2；
    所述金属元素M包括Na、Mg、Al、Li、Mn、Fe、Co、Ni、Cu或Zn中的一种或几种；所述负极材料中，金属元素M的含量从表面到核心逐渐减少，呈连续浓度梯度的掺杂分布；
    所述氧化亚硅/M复合材料的化学通式为SiM yO z，其中0<y<10，0<z<10。
  2. 根据权利要求1所述的含有金属元素梯度掺杂的负极材料，其特征在于，所述金属元素M在负极材料中的平均掺杂质量占所述负极材料总质量的5％-40％；
    其中，所述金属元素M的含量从表面的30％-50％到核心的0-20％呈连续浓度梯度递减。
  3. 根据权利要求2所述的含有金属元素梯度掺杂的负极材料，其特征在于，所述金属元素M的掺杂区域为由内向外占据负极材料颗粒半径[0-20％]至100％的区域。
  4. 根据权利要求1所述的含有金属元素梯度掺杂的负极材料，其特征在于，所述负极材料的颗粒平均粒径(D 50)为0.1-40μm；所述负极材料的颗粒比表面积为1m 2/g-40m 2/g。
  5. 根据权利要求1所述的含有金属元素梯度掺杂的负极材料，其特征在于，所述负极材料还包括：包覆在氧化亚硅/M复合材料颗粒外表面的碳质包覆层。
  6. 一种负极片，其特征在于，所述负极片包括上述权利要求1-5任一所述的负极材料。
  7. 一种锂电池，其特征在于，所述锂电池包括上述权利要求1-5任一所述的负极材料。
  8. 根据权利要求7所述的锂电池，其特征在于，所述锂电池具体包括液态锂离子电池、半固态锂离子电池、全固态离子电池或锂硫电池。
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