WO2023035343A1 - 一种用作锂离子电池负极的Zn-Ge-Cu-Si-P高熵合金材料及其制备方法 - Google Patents

一种用作锂离子电池负极的Zn-Ge-Cu-Si-P高熵合金材料及其制备方法 Download PDF

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WO2023035343A1
WO2023035343A1 PCT/CN2021/122054 CN2021122054W WO2023035343A1 WO 2023035343 A1 WO2023035343 A1 WO 2023035343A1 CN 2021122054 W CN2021122054 W CN 2021122054W WO 2023035343 A1 WO2023035343 A1 WO 2023035343A1
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powder
ball milling
stainless steel
ball mill
milling time
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韦雅庆
姚润哲
李会巧
陈永
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海南大学
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to the field of lithium-ion batteries, in particular to a Zn-Ge-Cu-Si-P high-entropy alloy material used as a negative electrode of a lithium-ion battery and a preparation method thereof.
  • Lithium-ion batteries stand out from the existing chemical power sources for their environmental friendliness, high energy conversion rate, and fast charging and discharging, and are considered to be the preferred power source for electric vehicles.
  • the low discharge capacity (372mAh/g) of traditional graphite anodes current lithium-ion power batteries are still far behind internal combustion engines in terms of energy density and power density, and cannot meet the needs of electric vehicle cruising range.
  • the negative electrode material is the key factor to improve the energy density of lithium-ion batteries and determine the performance of the battery. Target.
  • P element can react with metal Li to generate Li 3 P with multiple electrons, thus contributing a theoretical capacity of up to 2596mAh/g, which is 7 times that of graphite.
  • P element has abundant lithium storage and is cheap The characteristics of environmental protection are expected to become candidates for large-capacity anode materials.
  • the conductivity of red phosphorus in nature is extremely poor ( ⁇ 1 ⁇ 10 -14 S/cm)
  • the electrochemical lithium storage activity is low
  • the reversible capacity is less than 130mAh/g when used as an anode material
  • the first Coulombic efficiency is only 5%. Therefore, how to improve the conductivity and reactivity of red phosphorus has become a common problem faced by researchers.
  • Ge element which has lithium storage activity
  • the synthesized GeP x has excellent electronic conductivity ( ⁇ 2.4 ⁇ 10 6 S/m), comparable to graphite, much higher conductivity than its semiconductor Ge element and non-metal P element, showing typical metal conductivity characteristics.
  • GeP x can exhibit high reversible specific capacity (>1800mAh/g), ultra-high first Coulombic efficiency (ICE>90%) and stable and suitable voltage platform ( ⁇ 0.5V ). Nevertheless, it is worth noting that the price of Ge is as high as 7 million yuan/ton.
  • the present invention proposes a Zn-Ge-Cu-Si-P high-entropy alloy material used as a negative electrode of a lithium-ion battery and a preparation method thereof.
  • the Zn-Ge-P ternary alloy material Based on the Zn-Ge-P ternary alloy material, we replace part of the Zn and Ge elements with Cu and Si elements without changing the original crystal structure.
  • Si element can perform multi-electron alloying reaction with Li to contribute to higher discharge capacity.
  • Cu was chosen as an inert element mainly because of its excellent electrical conductivity to facilitate fast electron transport during lithiation.
  • the Zn-Ge-Cu-Si-P high entropy alloy material is synthesized.
  • the "synergistic effect" of high-entropy alloys is used to buffer the volume expansion between element components, improve electrical conductivity, and maintain the integrity of electrode morphology, thereby improving the cycle life and first-time Coulombic efficiency of the battery.
  • the above-mentioned high-entropy alloy is further compounded with carbon materials, and the mechanical flexibility, high conductivity and electrochemical stability of carbon materials are used to greatly improve the fast charge and fast discharge rate performance of the battery.
  • a preparation method for a Zn-Ge-Cu-Si-P high-entropy alloy material used as a lithium-ion battery negative electrode comprising the following steps:
  • Zinc powder, germanium powder, copper powder, silicon powder and red phosphorus are weighed according to target proportioning, and the mol ratio of described zinc powder, germanium powder, copper powder, silicon powder and red phosphorus is x: x: 1-x: 1-x: 2, 0 ⁇ x ⁇ 1, mix to get the powder material; put it into a stainless steel ball mill jar, put the stainless steel jar into a glove box filled with an inert atmosphere, remove the air inside the stainless steel jar, and make the jar The interior is filled with inert atmosphere Ar gas to prevent the oxidation of Zn, Ge, Si, Cu, P and other elements in the subsequent ball milling process, and the stainless steel jar is sealed and tightly sealed in the glove box;
  • step (3) The high-entropy Zn x Ge x Cu 1-x Si 1-x P 2 compound and carbon material prepared in step (2) are weighed according to the target proportion, added in a stainless steel ball mill jar, and the rotating speed of the ball mill is set to 350-450rpm, the single ball milling time is 0.8-1.2 hours, the interval is 20-40 minutes, and the number of repetitions is more than 10 times.
  • Zn composed of Zn x Ge x Cu 1-x Si 1-x P 2 compounds and carbon materials is obtained x Ge x Cu 1-x Si 1-x P 2 /C composites.
  • the x is 0.2 or 0.3 or 0.4 or 0.5 or 0.6 or 0.7 or 0.8.
  • step (2) the ball milling conditions: set the speed of the ball mill to 380-420rpm, the single ball milling time is 0.9-1.1 hours, the interval is 25-35 minutes, and the number of repetitions is 12-13 times.
  • the speed and ball milling time are better to provide sufficient collision shear force, sufficient reaction time and reaction energy for the reaction to ensure that the reaction continues.
  • the target ball milling time is insufficient, there will be a small amount of Zn, Ge, Cu, Si, P powder
  • the raw materials cannot be completely reacted; and when the target ball milling time is exceeded, additional energy and time will be consumed to increase costs, and excessive iron filings may be introduced; the function of "interval 25-35 minutes" is to perform positive-reverse for the instrument.
  • the switching of the rotation provides a buffer time, and also plays a role in protecting the instrument to a certain extent.
  • the rotational speed of the ball mill is set to 400 rpm
  • the single ball milling time is 1 hour
  • the interval is 30 minutes
  • the number of repetitions is 12 times, that is, the total ball milling time is 18 hours.
  • the ball milling conditions set the speed of the ball mill to 380-420rpm, the single ball milling time is 0.9-1.1 hours, the interval is 25-35 minutes, and the number of repetitions is 10-11 times.
  • the ball milling conditions better ensure that the high-entropy alloy and the carbon material are highly composited at the atomic level, rather than a simple physical mixing process.
  • the rotational speed of the ball mill is set to 400 rpm, the single ball milling time is 1 hour, the interval is 30 minutes, and the number of repetitions is 10 times, that is, the total ball milling time is 15 hours.
  • step (3) the mass ratio of the high-entropy Zn 0.5 Ge 0.5 Cu 0.5 Si 0.5 P 2 compound to the carbon material is 2:1.
  • step (1) and step (3) in the stainless steel ball milling tank, the ball-to-material ratio of the stainless steel beads and the powder material is 20:1, which better ensures that the ball milling process has sufficient collision shear force for the reaction to proceed. Provide enough energy.
  • preparation method includes the following steps:
  • Zinc powder, germanium powder, copper powder, silicon powder and red phosphorus are weighed according to the target ratio, and the molar ratio of zinc powder, germanium powder, copper powder, silicon powder and red phosphorus is 0.5:0.5: 0.5:0.5:2, mix to get the powder material; put it into the stainless steel ball mill tank, the ball material ratio of stainless steel beads and powder material is 20:1, put the stainless steel tank in the glove box with inert atmosphere, and grind the stainless steel in the glove box The jar is sealed tightly;
  • step (3) Weigh the Zn 0.5 Ge 0.5 Cu 0.5 Si 0.5 P 2 compound prepared in step (2) and the carbon material according to the target ratio, add it to the stainless steel ball mill jar, set the speed of the ball mill to 400rpm, and the single ball mill time 1 hour with an interval of 30 minutes, repeated 10 times, that is, the total ball milling time was 15 hours and the Zn 0.5 Ge 0.5 Cu 0.5 Si 0.5 P 2 /C composite material was obtained after ball milling.
  • a lithium-ion battery multi-component high-entropy alloy negative electrode material and its preparation method proposed by the present invention have simple process, low cost, can be synthesized and prepared in batches, and are easy to produce and synthesize on a large scale. Compared with existing similar products, the present invention has the following advantages advantage:
  • this experiment synthesized multivariate high-entropy alloys by using elements such as Zn, Cu, Si, and P, which are rich in resources and low in price.
  • the material cost is greatly reduced on the basis of the performance level, and it is easy to be prepared, popularized and used on a large scale.
  • the present invention adopts the high-energy ball milling method to synthesize and prepare the high-entropy alloy negative electrode material, which can be carried out at normal temperature and pressure, with less energy consumption, high yield, high product purity, cost saving, and easy large-scale promotion and preparation.
  • the series of multi-component high-entropy alloys developed by the present invention have higher reactivity, larger discharge capacity and excellent reversibility, and the first Coulombic efficiency is as high as 90%, directly reaching commercial
  • the level of lithiation avoids the pre-lithiation process, and solves the application problems of poor reversibility and low Coulombic efficiency ( ⁇ 75%) of traditional alloy-type negative electrode materials.
  • the series of high-entropy alloys developed by the present invention are short-range disordered amorphous amorphous materials. Compared with the high-crystalline state, its amorphous structure is more conducive to slowing down the stress and strain of the structure during the lithiation process, buffering volume Expansion, with more excellent cycle stability.
  • the series of Zn-Ge-Cu-Si-P high-entropy alloys proposed by the present invention has no definite stoichiometric ratio among the elements, its element composition and ratio can be adjusted arbitrarily, and it has a wide solid solution range, which is Tuning the conductivity and reversible capacity of the electrode sheet provides great flexibility unmatched by other compounds with fixed stoichiometry.
  • the traditional alloy-type negative electrode materials will face the problems of low electronic conductivity, volume expansion and pulverization and shedding of active material particles during the lithiation process, resulting in material failure and rapid capacity decay.
  • the high-energy ball milling method proposed by the present invention combines conductive carbon materials and active materials to prepare composite materials of high-entropy alloys and carbon materials.
  • the high conductivity, mechanical flexibility and chemical stability of carbon materials can be used to promote active materials in lithium Electron transport during the chemicalization process suppresses volume expansion, thereby maintaining the integrity of the morphology and greatly improving the cycle stability and service life of the battery.
  • the carbon composite method can also be applied to improve the cycle life and electrochemical performance of other alloy-type anode materials.
  • Fig. 1 2288 in Fig. 1, Fig. 3 and Fig. 5 represents Zn 0.2 Ge 0.2 Cu 0.8 Si 0.8 P 2
  • 3377 represents Zn 0.3 Ge 0.3 Cu 0.7 Si 0.7 P 2
  • 4466 represents Zn 0.4 Ge 0.4 Cu 0.6 Si 0.6 P 2
  • 5555 represents Zn 0.5 Ge 0.5 Cu 0.5 Si 0.5 P 2
  • 6644 represents Zn 0.6 Ge 0.6 Cu 0.4 Si 0.4 P 2
  • 7733 represents Zn 0.7 Ge 0.7 Cu 0.3 Si 0.3 P 2
  • 8822 represents Zn 0.8 Ge 0.8 Si Cu 0.2 2 .
  • the present invention mainly synthesizes the multi-element alloy negative electrode material and its carbon composite material through the high-energy ball milling method, and its preparation method mainly includes the following steps: (taking Zn 0.5 Ge 0.5 Cu 0.5 Si 0.5 P 2 as an example)
  • Example 1 the molar ratios of zinc powder, germanium powder, copper powder, silicon powder and red phosphorus were adjusted to prepare Zn 0.8 Ge 0.8 Cu 0.2 Si 0.2 P 2 , Zn 0.7 Ge 0.7 Cu 0.3 Si 0.3 P 2 , Zn 0.6 Ge 0.6 Cu 0.4 Si 0.4 P 2 , Zn 0.4 Ge 0.4 Cu 0.6 Si 0.6 P 2 , Zn 0.3 Ge 0.3 Cu 0.7 Si 0.7 P 2 , Zn 0.2 Ge 0.2 Cu 0.8 Si 0.8 P 2 high entropy alloy materials.
  • the short-range disordered amorphous feature of this type of high-entropy alloy can slow down the structural stress and strain during the lithiation process to a certain extent, thereby reducing the powdering and falling off of particles, and maintaining the integrity of the electrode morphology. Compared with the high crystalline state , and its amorphous characteristics can make the battery have good cycle stability and electrochemical performance.
  • the primary particle size of the high-entropy alloy is about 200-300nm. Further analysis from the high-resolution HRTEM images shows that no obvious lattice fringes are observed, which further verifies the high-entropy alloy. Amorphous character of short-range disorder in entropy alloys. It can be seen from the SEM image of the scanning electron microscope that the morphology of the high-entropy alloy is composed of primary nanoparticles agglomerated into micron-sized secondary particles. The diameter of the particles ranges from one micron to several microns. No rules. By analyzing its elements, it can be seen from the EDS images that Zn, Ge, Si, Cu, and P elements are evenly distributed, showing a highly composite state at the atomic level, rather than simple physical mixing, indicating that the raw materials have been completely reacted.
  • the battery As shown in Figure 5, at a current density of 100mA/g, the battery is continuously charged and discharged at a constant current. After 20 cycles, the battery capacity decays, and the capacity retention rate of the Zn 0.8 Cu 0.2 Ge 0.8 Si 0.2 P 2 /C system is the highest , at 90.7%, with excellent cycle stability and electrochemical performance.
  • step 3. specifically:
  • Example 3 The results show that the XRD of the Zn 0.5 Ge 0.5 Cu 0.5 Si 0.5 P 2 compound obtained in Example 3 is still a pure phase, and the TEM spectrum is unchanged from Example 1, and the primary particle size of the high-entropy alloy is still about 200-300nm. Further analysis from the high-resolution HRTEM image shows that no obvious lattice fringes are observed, and the electrochemical performance of the synthesized Zn 0.5 Ge 0.5 Cu 0.5 Si 0.5 P 2 /C has a first discharge capacity of 1680mAh/g and a first coulombic efficiency of 90.1% , no significant difference with Example 1, but increasing the ball milling time increases unnecessary loss.
  • step 2 adjust the ball milling time of step 2., specifically:
  • Example 5 The results show that the electrochemical performance of the Zn 0.5 Ge 0.5 Cu 0.5 Si 0.5 P 2 /C composite material obtained in Example 5 is not significantly different from that of Example 1, wherein the first discharge capacity is 1700mAh/g, and the first coulombic efficiency is 89.3%. It shows that after more than 15 hours of ball milling, the material has been completely uniformly compounded, and there is no need to increase the time of ball milling compound C.
  • Zn 0.33 Ge 0.33 Cu 0.33 P 2 /C composite material was prepared by mixing zinc powder, germanium powder, copper powder and red phosphorus in a molar ratio of 0.33:0.33:0.33:2, referring to the process conditions of Example 1.
  • Zn 0.33 Ge 0.33 Si 0.33 P 2 /C composite material was prepared by mixing zinc powder, germanium powder, silicon powder and red phosphorus in a molar ratio of 0.33:0.33:0.33:2, referring to the process conditions of Example 1.

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Abstract

本发明提供一种用作锂离子电池负极的Zn-Ge-Cu-Si-P高熵合金材料及其制备方法，将锌粉、锗粉、铜粉、硅粉和红磷按照目标配比进行称量，所述锌粉、锗粉、铜粉、硅粉和红磷的摩尔比为x：x：1-x：1-x：2，0<x<1，球磨后获得由Zn、Ge、Cu、Si、P元素形成的高熵Zn xGe xCu 1-xSi 1-xP 2化合物；将高熵Zn xGe xCu 1-xSi 1-xP 2化合物与碳材料混合，球磨后获得Zn xGe xCu 1-xSi 1-xP 2/C复合材料。该材料具有放电比容量大，首次库伦效率高，可逆性好，电化学性能优异，低成本等优点。

Description

一种用作锂离子电池负极的Zn-Ge-Cu-Si-P高熵合金材料及其制备方法 技术领域
本发明涉及锂离子电池领域，特别涉及一种用作锂离子电池负极的Zn-Ge-Cu-Si-P高熵合金材料及其制备方法。
背景技术
锂离子电池以其环境友好，能量转换率高，可快速充放电等优点在现有化学电源中脱颖而出，被认为是电动汽车的首选电源。然而，受限于传统石墨负极的低放电容量(372mAh/g)，当前锂离子动力电池在能量密度、功率密度上与内燃机相比还相差甚远，不能满足电动汽车续航里程的需求。作为核心组成部分之一，负极材料是提高锂离子电池能量密度并决定电池性能优劣的关键因素，因此，开发大容量、高性能的负极材料是目前学术界和工业界面临的首要任务和共同目标。
相比石墨而言，P元素可以与金属Li进行多电子反应生成Li 3P，从而贡献出高达2596mAh/g的理论容量，是石墨的7倍之多，加上P元素的储锂丰富，廉价环保的特点，有望成为大容量负极材料的候选者。然而，自然界中红磷的导电性极差(<1×10 -14S/cm)，电化学储锂活性低，用作负极材料时可逆容量不到130mAh/g，首次库伦效率仅为5％。因此，如何提高红磷的导电性和反应活性成为研究者们面临的共同难题。为此，有人提出将本身具有储锂活性的Ge元素引入到P中，开发出一类新型双活性组分的P-Ge化合物，合成出来的GeP x具有优异的电子导电率(～2.4×10 6S/m)，可以跟石墨相媲美，比其半导体Ge单质和非金属P单质的导电性要高许多，呈现出典型的金属导电性特征。当用作锂离子电池负极材料时，GeP x能够表现出较高的可逆比容量(>1800mAh/g)，超高的首次库伦效率(ICE>90％)和稳定合适的电压平台(～0.5V)。尽管如此，值得注意的是，Ge的价格高达700万元/吨，随着GeP x中Ge比例的增多，原材料的成本价格也越来越昂贵，会极大地阻碍P基合金负极材料的进一步实用化和产业化。进而有人以Zn元素取代部分Ge元素开发出Zn-Ge-P三元合金材料，一方 面降低了Ge元素的用量降低了成本，另一方面Zn元素也具有储锂活性，不会降低原材料的高容量。但Zn-Ge-P三元合金材料性能上也有较大提高空间。
发明内容
鉴于此，本发明提出一种用作锂离子电池负极的Zn-Ge-Cu-Si-P高熵合金材料及其制备方法。
基于Zn-Ge-P三元合金材料，我们以Cu，Si元素取代部分Zn，Ge元素，取代的同时也不改变其原本的晶体结构。Si元素可以与Li进行多电子合金化反应贡献出较高的放电容量。选择Cu惰性元素主要因为它具有优异的导电性促进锂化过程中的电子快速传输。从而合成Zn-Ge-Cu-Si-P高熵合金材料。利用高熵合金的“协同效应”来缓冲元素组分间的体积膨胀，提高导电性，维持电极形貌的完整，从而改善电池的循环寿命和首次库伦效率。此外，将上述高熵合金进一步与碳材料复合，利用碳材料的机械柔性、高导电性和电化学稳定性极大提升了电池的快充快放倍率性能。
本发明的技术方案是这样实现的：
一种用作锂离子电池负极的Zn-Ge-Cu-Si-P高熵合金材料的制备方法，包括以下步骤：
(1)将锌粉、锗粉、铜粉、硅粉和红磷按照目标配比进行称量，所述锌粉、锗粉、铜粉、硅粉和红磷的摩尔比为x：x：1-x：1-x：2，0<x<1，混合即得粉末材料；加入不锈钢球磨罐中，将不锈钢罐子放入充满惰性气氛的手套箱中，排除不锈钢罐子内部的空气，使罐子内部充满惰性气氛Ar气，防止后续球磨过程中Zn、Ge、Si、Cu、P等元素发生氧化，在手套箱内对不锈钢罐子进行封装盖紧；
(2)将不锈钢罐子取出手套箱，安装到球磨机上进行固定和拧紧，设置球磨机的转速为350-450rpm，单次球磨时间0.8-1.2小时，间隔20-40分钟，重复次数12次以上，球磨后获得由Zn、Ge、Cu、Si、P元素形成的高熵Zn xGe xCu 1-xSi 1-xP 2化合物；
(3)将步骤(2)制得的高熵Zn xGe xCu 1-xSi 1-xP 2化合物与碳材料按照目标配比进行称量，加入不锈钢球磨罐中，设置球磨机的转速为350-450rpm，单次 球磨时间0.8-1.2小时，间隔20-40分钟，重复次数10次以上，球磨后获得由Zn xGe xCu 1-xSi 1-xP 2化合物与碳材料组成的Zn xGe xCu 1-xSi 1-xP 2/C复合材料。
进一步的，所述x为0.2或0.3或0.4或0.5或0.6或0.7或0.8。
进一步的，步骤(2)中，所述球磨条件：设置球磨机的转速为380-420rpm，单次球磨时间0.9-1.1小时，间隔25-35分钟，重复次数12-13次。该转速以及球磨时间更好为反应提供足够的碰撞剪切力、足够的反应时间和反应能量，保证反应持续进行，目标球磨时间不足时，会有少量的Zn、Ge、Cu、Si、P粉等原料没法完全反应；而超出目标球磨时间时，会消耗额外的能量和时间增加成本，并且可能会引入过多的铁屑杂质；“间隔25-35分钟”作用是为仪器进行正-反转的切换提供缓冲时间，也在一定程度上起到保护仪器的作用。
优选地，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数12次，即总计球磨时间18小时。
进一步的，步骤(3)中，所述球磨条件：设置球磨机的转速为380-420rpm，单次球磨时间0.9-1.1小时，间隔25-35分钟，重复次数10-11次。该球磨条件更好确保高熵合金与碳材料呈原子级高度复合状态，而非简单的物理混料过程。优选地，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数10次，即总计球磨时间15小时。
进一步的，步骤(3)中，所述高熵Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物与碳材料的质量比为2：1。
进一步的，步骤(1)、步骤(3)中，不锈钢球磨罐中，不锈钢珠子与粉末材料的球料比为20:1，更好保证球磨过程有足够的碰撞剪切力，为反应的进行提供足够的能量。
进一步的，所述的制备方法，包括以下步骤：
(1)将锌粉、锗粉、铜粉、硅粉和红磷按照目标配比进行称量，所述锌粉、锗粉、铜粉、硅粉和红磷的摩尔比为0.5：0.5：0.5：0.5：2，混合即得粉末材料；加入不锈钢球磨罐中，不锈钢珠子与粉末材料的球料比为20:1，将不锈钢罐子放入惰性气氛的手套箱中，在手套箱内对不锈钢罐子进行封装盖紧；
(2)将不锈钢罐子取出手套箱，安装到球磨机上进行固定和拧紧，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数12次， 即总计球磨时间18小时，球磨后获得由Zn、Ge、Cu、Si、P元素形成的高熵Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物；
(3)将步骤(2)制得的Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物与碳材料按照目标配比进行称量，加入不锈钢球磨罐中，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数10次，即总计球磨时间15小时球磨后获得Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2/C复合材料。
与现有技术相比，本发明的有益效果是：
本发明提出的一种锂离子电池多元高熵合金负极材料及其制备方法，工艺简单，成本低，可以批量合成制备，易于大规模生产合成，相比于现有的同类产品，本发明具有以下优点：
①相比于传统价格昂贵的过渡金属元素(Co、Mn、Ru等)，本实验采用资源丰富、价格低廉的Zn、Cu、Si、P等元素合成出多元高熵合金，在保持同等电化学性能水平的基础上极大地降低了材料成本，易于大规模制备推广和使用。
②本发明采用高能球磨法合成制备高熵合金负极材料，可以在常温常压下进行，耗能少，产率高，产物纯度高，节约成本，易于大规模推广与制备。
③相比于传统合金型单质或二元合金，本发明开发的系列多元高熵合金具有较高的反应活性，较大的放电容量和优异的可逆性，首次库伦效率高达90％，直接达到商业化水平，避免了预锂化工艺，解决了传统合金型负极材料可逆性差、库伦效率低(<75％)的应用难题。
④本发明开发的系列Zn-Ge-Cu-Si-P高熵合金具有热力学上的“高熵效应”和性能上的“鸡尾酒效应”及“溢出效应”，活性元素Zn-Ge-Si-P贡献容量，高导电性元素Cu促进电子快速传导，元素组分间分阶段、多层次、多平台的“协同作用”极大地提高电池的电化学性能。
⑤本发明开发的系列高熵合金呈短程无序的无定形非晶态材料，相比于高结晶态而言，其非晶态结构更有利于减缓锂化过程中结构的应力应变，缓冲体积膨胀，具有更为优异的循环稳定性。
⑥本发明提出的系列Zn-Ge-Cu-Si-P高熵合金在各元素间并没有明确的化学计量比，其元素成分可调、比例任意可调，具有较宽的固溶范围，为 调节电极片的导电性和可逆容量提供很大的灵活性，是其他固定化学计量比的化合物所无法比拟的。
⑦传统的合金型负极材料在锂化过程中会面临着电子导电率低，活性物质颗粒体积膨胀和粉化脱落问题，导致材料失效和容量快速衰减。本发明提出的采用高能球磨法将导电碳材料与活性材料进行复合，制备出高熵合金与碳材料的复合材料，可以利用碳材料的高导电性、机械柔性和化学稳定性促进活性材料在锂化过程中的电子传输，抑制体积膨胀，从而维护形貌的完整，极大地提高电池循环稳定性和使用寿命。该碳复合的方法也能够应用于提升其他合金型负极材料的循环寿命和电化学性能。
附图说明
图1.Zn-Ge-Cu-Si-P高熵合金材料的XRD数据图谱；
图2.Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2的HRTEM、SEM和元素分布图；
图3.Zn-Ge-Cu-Si-P/C高熵合金材料电导率图；
图4.Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2/C充放电曲线；
图5.Zn-Ge-Cu-Si-P/C高熵合金材料的循环寿命曲线。
其中，图1、图3、图5中2288代表Zn 0.2Ge 0.2Cu 0.8Si 0.8P 2，3377代表Zn 0.3Ge 0.3Cu 0.7Si 0.7P 2，4466代表Zn 0.4Ge 0.4Cu 0.6Si 0.6P 2，5555代表Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2，6644代表Zn 0.6Ge 0.6Cu 0.4Si 0.4P 2，7733代表Zn 0.7Ge 0.7Cu 0.3Si 0.3P 2，8822代表Zn 0.8Ge 0.8Cu 0.2Si 0.2P 2。
具体实施方式
为了更好理解本发明技术内容，下面提供具体实施例，对本发明做进一步的说明。
本发明实施例所用的实验方法如无特殊说明，均为常规方法。
本发明实施例所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1
本发明主要通过高能球磨法合成多元合金负极材料及其碳复合材料，其制备方法主要包括以下步骤：(以Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2为例)
①将锌粉、锗粉(Macklin，99.999％)、铜粉(Macklin，99.9％)、硅粉(Aladdin，99.9％)和红磷(Macklin，AR98.5％)按照特定的摩尔比(1：1：1：1：4)进行称量和配比，加入不锈钢球磨罐中，不锈钢珠子和粉末材料的球料比为20:1，将不锈钢罐子放入充满惰性气氛(Ar气保护)的手套箱中(无水无氧，水氧含量均<1ppm)，在手套箱内对不锈钢罐子进行封装盖紧(用锁紧装置进行锁紧和密封)。
②将不锈钢罐子取出手套箱，安装到球磨机上进行固定和拧紧，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数12次，即总计球磨时间18小时，即可获得由Zn、Ge、Cu、Si、P元素形成的高熵Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物。
③将步骤②制得的高熵Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物与碳材料(SuperP)按照既定的质量比(6:3)进行称量，加入不锈钢球磨罐中，不锈钢珠子和粉末材料的球料比为20:1，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数10次，即总计球磨时间15小时，即可获得由Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物与碳材料组成的Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2/C复合材料。
实施例2
参照实施例1的制备方法，调整锌粉、锗粉、铜粉、硅粉和红磷摩尔比，分别制备Zn 0.8Ge 0.8Cu 0.2Si 0.2P 2、Zn 0.7Ge 0.7Cu 0.3Si 0.3P 2、Zn 0.6Ge 0.6Cu 0.4Si 0.4P 2、Zn 0.4Ge 0.4Cu 0.6Si 0.6P 2、Zn 0.3Ge 0.3Cu 0.7Si 0.7P 2、Zn 0.2Ge 0.2Cu 0.8Si 0.8P 2高熵合金材料。
Figure PCTCN2021122054-appb-000001
Figure PCTCN2021122054-appb-000002
将上述实施例得到的材料进行检测，结果如下：
(1)合成的Zn-Ge-Cu-Si-P高熵合金材料的X-射线衍射图谱
如图1所示，从衍射图谱中可以看出，合成出来的高熵合金均与ZnGeP 2衍射峰一致，各组分单质元素的衍射峰均已消失，说明材料已经完全反应，具有较高的产率和纯度。并且随着Zn，Ge含量的减少，因为Si的原子半径比Ge小，随着Si取代含量的增加，Ge含量减小，势必会引起材料晶格晶胞的收缩，从而晶胞参数减少。根据布拉格公式规律，衍射峰往高角度偏移。这类高熵合金短程无序的非晶态特征在一定程度上可以减缓锂化过程中的结构应力应变，从而减少颗粒的粉化脱落，维护电极形貌完整，相比于高结晶态而言，其非晶态特征更能使电池拥有良好的循环稳定性和电化学性能。
(2)对合成的Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2高熵合金进行透射电子显微镜(TEM)分析
如图2所示，从低倍TEM图像观察到，高熵合金的一次颗粒粒径大概在200-300nm左右，从高分辨HRTEM图像进一步分析，没有观察到明显的晶格 条纹，进一步验证了高熵合金短程无序的非晶态特征。从扫描电子显微镜SEM图像可以看出，该高熵合金的形貌是由一次纳米颗粒团聚为微米级的二次粒子组成，颗粒直径从一微米到几微米不等，其表面形貌、形状均无规则。对其元素进行分析，从EDS图像可以看出Zn、Ge、Si、Cu、P元素均匀分布，呈现出原子级的高度复合状态，而非简单的物理混合，表明其原料均已完全反应。
(3)Zn-Ge-Cu-Si-P/C高熵合金材料电导率
如图3所示，从Zn-Ge-Cu-Si-P/C高熵合金材料的电导率图中可以看出，随着掺杂的Cu元素的含量的增加，Zn-Ge-Cu-Si-P/C高熵合金材料的电导率在不断提高，说明加入惰性Cu元素提高了材料的导电性。
(4)对合成的系列高熵合金负极材料进行电化学性能测试
如图4所示，以Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2/C为例，其首次放电容量高达1695mAh/g，是商业石墨负极材料(372mAh/g)的4倍之多。值得一提的是，此类高熵合金负极材料的首次充电容量为1511mAh/g，首次库伦效率为89.2％，具有很高的反应活性和可逆性，基本达到商业化水平，避免了预锂化工艺，直接解决了传统合金型负极材料可逆性差、库伦效率低(<75％)的应用难题。
(5)对合成出来的Zn-Ge-Cu-Si-P/C高熵合金材料进行长循环性能测试
如图5所示，在100mA/g的电流密度下，对电池持续恒流充放电，经过20圈后电池容量衰减，其中Zn 0.8Cu 0.2Ge 0.8Si 0.2P 2/C体系的容量保持率最高，在90.7％，具有优异的循环稳定性和电化学性能。
实施例3
在实施例1的基础，调整步骤②、步骤③的球磨时间，具体为：
②将不锈钢罐子取出手套箱，安装到球磨机上进行固定和拧紧，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数13次，即总计球磨时间19.5小时，即可获得由Zn、Ge、Cu、Si、P元素形成的高熵Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物。
③将步骤②制得的高熵Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物与碳材料(SuperP)按照既定的质量比(6:3)进行称量，加入不锈钢球磨罐中，不锈钢珠子和粉末材料的球料比为20:1，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数11次，即总计球磨时间16.5小时，即可获得由Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物与碳材料组成的Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2/C复合材料。
结果显示，实施例3得到Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物的XRD仍然是纯相，且TEM图谱与实施例1无变化，高熵合金的一次颗粒粒径仍在200-300nm左右，从高分辨HRTEM图像进一步分析，没有观察到明显的晶格条纹，同时合成的Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2/C的电化学性能首次放电容量为1680mAh/g，首次库伦效率为90.1％，与实施例1无明显区别，但是增长了球磨时间增加了不必要的损耗。
实施例4
在实施例1的基础，调整步骤②的球磨时间，具体为：
②将不锈钢罐子取出手套箱，安装到球磨机上进行固定和拧紧，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数14次，即总计球磨时间21小时，即可获得由Zn、Ge、Cu、Si、P元素形成的高熵Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物。
结果显示，实施例4球磨得到Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物的XRD仍然是纯相，与实施例1得到的产物无明显差别，其电化学性能也无明显差异，但增长球磨时间增加了能量和仪器的损耗，因此说明实施例1的球磨时间为最佳。
实施例5
在实施例1的基础，在实施例1的基础，调整步骤③的球磨时间，具体为：
③将步骤②制得的高熵Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物与碳材料(SuperP)按照既定的质量比(6:3)进行称量，加入不锈钢球磨罐中，不锈钢珠子和粉末材料的球料比为20:1，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数12次，即总计球磨时间18小时，即可获得由Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物与碳材料组成的Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2/C复合材料。
结果显示，实施例5得到的Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2/C复合材料的电化学性能与实施例1无明显差别，其中，首次放电容量1700mAh/g，首次库伦效率为89.3％。说明球磨超过15小时后，材料已经完全均匀复合，没有再增加球磨复合C的时间的必要。
对比例1
在实施例1基础上，没有加入硅粉，原料配比：
取锌粉、锗粉、铜粉和红磷的摩尔比0.33：0.33：0.33：2混合，参照实施例1的工艺条件，制成Zn 0.33Ge 0.33Cu 0.33P 2/C复合材料。
结果显示，对比例1合成的Zn 0.33Ge 0.33Cu 0.33P 2/C复合材料的首次放电容量仅为1300mAh/g，与实施例1相比大大下降，这是因为缺少了Si元素提供容量(Si与Li反应生成Li 22Si 5)。
对比例2
在实施例1基础上，没有加入铜粉，原料配比：
取锌粉、锗粉、硅粉和红磷的摩尔比0.33：0.33：0.33：2混合，参照实施例1的工艺条件，制成Zn 0.33Ge 0.33Si 0.33P 2/C复合材料。
结果显示，对比例2制成Zn 0.33Ge 0.33Si 0.33P 2/C复合材料的电子电导率由于缺少惰性Cu元素(能够提高材料的导电性)相比于实施例1大大下降(由于电阻过大，四探针法无法测得其电导率)。
对比例3
在实施例1的基础，在实施例1的基础，调整步骤②的球磨时间，具体为
②将不锈钢罐子取出手套箱，安装到球磨机上进行固定和拧紧，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数11次，即总计球磨时间16.5小时，即可获得由Zn、Ge、Cu、Si、P元素形成的高熵Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物。
结果显示，对比例3得到Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物的XRD图谱仍然含有Si单质的杂峰，说明球磨时间不够，反应物仍未完全反应，缩短球磨时间无法得到纯相产物，所以需要增加球磨时间，说明实施例1的球磨时间为最佳。
对比例4
在实施例1的基础，在实施例1的基础，调整步骤③的球磨时间，具体为
③将步骤②制得的高熵Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物与碳材料(SuperP)按照既定的质量比(6:3)进行称量，加入不锈钢球磨罐中，不锈钢珠子和粉末材料的球料比为20:1，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数3次，即总计球磨时间4小时，即可获得由Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2 化合物与碳材料组成的Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2/C复合材料。
结果显示，对比例5得到的复合材料达不到预期效果，Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物与碳材料未能实现原子级的高度均匀复合，相比与实施例1所得的Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2/C复合材料，球磨时间过短的复合材料的电池循环性能大大下降，并且首次放电容量在1250mAh/g，相比于1695mAh/g有明显下降，说明过短的复合C的球磨时间无法得到预期提高电化学性能的效果。
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 (10)

  1. 一种用作锂离子电池负极的Zn-Ge-Cu-Si-P高熵合金材料的制备方法，其特征在于，包括以下步骤：
    (1)将锌粉、锗粉、铜粉、硅粉和红磷按照目标配比进行称量，所述锌粉、锗粉、铜粉、硅粉和红磷的摩尔比为x：x：1-x：1-x：2，0<x<1，混合即得粉末材料；加入不锈钢球磨罐中，将不锈钢罐子放入惰性气氛的手套箱中，在手套箱内对不锈钢罐子进行封装盖紧；
    (2)将不锈钢罐子取出手套箱，安装到球磨机上进行固定和拧紧，设置球磨机的转速为350-450rpm，单次球磨时间0.8-1.2小时，间隔20-40分钟，重复次数12次以上，球磨后获得由Zn、Ge、Cu、Si、P元素形成的高熵Zn xGe xCu 1-xSi 1-xP 2化合物；
    (3)将步骤(2)制得的Zn xGe xCu 1-xSi 1-xP 2化合物与碳材料按照目标配比进行称量，加入不锈钢球磨罐中，设置球磨机的转速为350-450rpm，单次球磨时间0.8-1.2小时，间隔20-40分钟，重复次数10次以上，球磨后获得Zn xGe xCu 1-xSi 1-xP 2/C复合材料。
  2. 根据权利要求1所述的制备方法，其特征在于，所述x为0.2或0.3或0.4或0.5或0.6或0.7或0.8。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤(2)中，所述球磨条件：设置球磨机的转速为380-420rpm，单次球磨时间0.9-1.1小时，间隔25-35分钟，重复次数12-13次。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤(3)中，所述球磨条件：设置球磨机的转速为380-420rpm，单次球磨时间0.9-1.1小时，间隔25-35分钟，重复次数10-11次。
  5. 根据权利要求3所述的制备方法，其特征在于，步骤(2)中，所述球磨条件：设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数12次，即总计球磨时间18小时。
  6. 根据权利要求4所述的制备方法，其特征在于，步骤(3)中，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数10次，即总计球磨时间15小时。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤(3)中，所述Zn xGe xCu 1-xSi 1-xP 2化合物与碳材料的质量比为2：1。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤(1)、步骤(3)中，不锈钢球磨罐中，不锈钢珠子与粉末材料的球料比为20:1。
  9. 根据权利要求1所述的制备方法，其特征在于，包括以下步骤：
    (1)将锌粉、锗粉、铜粉、硅粉和红磷按照目标配比进行称量，所述锌粉、锗粉、铜粉、硅粉和红磷的摩尔比为0.5：0.5：0.5：0.5：2，混合即得粉末材料；加入不锈钢球磨罐中，不锈钢珠子与粉末材料的球料比为20:1，将不锈钢罐子放入惰性气氛的手套箱中，在手套箱内对不锈钢罐子进行封装盖紧；
    (2)将不锈钢罐子取出手套箱，安装到球磨机上进行固定和拧紧，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数12次，即总计球磨时间18小时，球磨后获得由Zn、Ge、Cu、Si、P元素形成的高熵Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物；
    (3)将步骤(2)制得的Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2化合物与碳材料按照目标配比进行称量，加入不锈钢球磨罐中，设置球磨机的转速为400rpm，单次球磨时间1小时，间隔30分钟，重复次数10次，即总计球磨时间15小时球磨后获得Zn 0.5Ge 0.5Cu 0.5Si 0.5P 2/C复合材料。
  10. 一种用作锂离子电池负极的Zn-Ge-Cu-Si-P高熵合金材料，其特征在于，由权利要求1-9任一项所述的制备方法制得。
PCT/CN2021/122054 2021-09-10 2021-09-30 一种用作锂离子电池负极的Zn-Ge-Cu-Si-P高熵合金材料及其制备方法 WO2023035343A1 (zh)

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