CN113046597A - Lithium ion battery multi-element alloy negative electrode material and preparation method thereof - Google Patents
Lithium ion battery multi-element alloy negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a multi-element alloy cathode material of a lithium ion battery and a preparation method thereof, wherein the preparation method comprises the following steps: (1) zinc powder, germanium powder and red phosphorus are mixed according to a molar ratio x: y: z, mixing, adding y to z-x into a stainless steel ball milling tank, putting the stainless steel tank into a glove box filled with inert atmosphere, and sealing and tightly covering the stainless steel tank in the glove box; (2) Taking the stainless steel tank out of the glove box, installing the glove box on a ball mill for fixing and screwing, wherein the rotating speed of the ball mill is 380-450rpm/min, the single ball milling time is 0.9-1.1 hours, the interval is 10-20 minutes, the repetition times are 11-13 times, and the total ball milling time is 12-13 hours, thus obtaining the ternary Zn formed by Zn, Ge and P elementsxGeyPzA compound is provided. By adopting the preparation method, the use of Ge can be effectively reduced, the preparation method is friendly to Ge resources, the cost is effectively reduced, and the material prepared on the basis also has the advantages of large specific discharge capacity, high first coulombic efficiency, good reversibility, excellent electrochemical performance and the like.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery multi-element alloy cathode material and a preparation method thereof.
Background
The lithium ion battery is distinguished from the existing chemical power supply by the advantages of environmental friendliness, high energy conversion rate, rapid charge and discharge and the like, and is considered as a preferred power supply of the electric automobile. However, limited by the low discharge capacity (372mAh/g) of the conventional graphite cathode, the energy density and power density of the current lithium ion power battery are far from those of the internal combustion engine, and the current lithium ion power battery cannot meet the requirement of the endurance mileage of the electric vehicle. As one of the core components, the negative electrode material is a key factor for increasing the energy density of the lithium ion battery and determining the performance of the battery, and therefore, developing a high-capacity and high-performance negative electrode material is a primary task and a common target in the academic and industrial fields at present.
Compared with graphite, P element can perform multi-electron reaction with metallic Li to generate Li3P, thereby contributing to the theoretical capacity of 2596mAh/g, which is 7 times as much as that of graphite, and being expected to become a candidate of a high-capacity cathode material due to the characteristics of rich lithium storage, low price and environmental protection of the P element. However, red phosphorus in nature has very poor conductivity (<1×10-14S/cm), the electrochemical lithium storage activity is low, the reversible capacity is less than 130mAh/g when the lithium storage material is used as a negative electrode material, and the first coulombic efficiency is only 5%. Therefore, how to improve the conductivity and reactivity of red phosphorus is a common problem for researchers. For this reason, it has been proposed to introduce Ge element, which itself has lithium storage activity, into P, to develop a new class of P-Ge compounds with dual active components, and to synthesize GePxHas excellent electronic conductivity (2.4 multiplied by 10)6S/m), which is comparable to graphite, has much higher conductivity than the Ge elementary substance and the P elementary substance, and shows typical metal conductivity characteristics. GeP when used as a negative electrode material for lithium ion batteriesxCan show higher reversible specific capacity (>1800mAh/g), ultra-high first coulombic efficiency (ICE)>90%) and a stable suitable voltage plateau (0.5V). However, it is worth noting that the price of Ge is up to 700 ten thousand yuan/ton, with GePxThe proportion of medium Ge is increased, the cost price of raw materials is more and more expensive, and further practical application and industrialization of the P-based alloy negative electrode material are greatly hindered.
Disclosure of Invention
Based on the above, the invention provides a lithium ion battery multi-element alloy cathode material and a preparation method thereof. The invention aims to reduce GeP aiming at the shortages and the improvement requirements of the existing materials on cost pricexThe use amount and cost of Ge in the alloy are reduced, Zn, Si, Cu and the like are used for partially or completely replacing Ge, and the Zn-Ge-P, Zn-Si-P, Cu-Si-P ternary alloy material is developed. On one hand, Zn, Si and Cu are in adjacent elements with Ge in the periodic table, the atomic radius and the electronegativity are very similar, and preconditions are provided for replacing partial Ge sites and reducing the Ge content. On the other hand, Zn and Si have lithium storage activity and can be used in combination with Li+Alloying to generate LiZn and LixSi alloy, which contributes extra capacity to the electrode without lowering GePxOriginal high reversible capacity. More importantly, the reserves of the raw materials of Zn, Si and Cu are rich, the price of Zn is only 1.2 ten thousand yuan/ton, and the Zn is 1/600 of Ge, so that the preparation cost of the raw materials can be greatly reduced, and the further development and application of the P-based negative electrode material are promoted. The invention aims to prepare the multi-element Zn-Ge-P, Zn-Si-P, Cu-Si-P alloy material, and aims to obtain the lithium ion battery cathode material with large specific capacity, high reversibility, good rate capability and excellent cycle performance, reduce the price cost of the material on the basis and promote the commercial application and development of the alloy cathode material.
The technical scheme of the invention is realized as follows:
a preparation method of a lithium ion battery multi-element alloy cathode material comprises the following steps:
(1) zinc powder, germanium powder and red phosphorus are mixed according to a molar ratio x: y: and z, mixing, adding y to z-x into a stainless steel ball milling tank, putting the stainless steel tank into a glove box filled with inert atmosphere, and sealing and tightly covering the stainless steel tank in the glove box.
(2) Taking the stainless steel tank out of the glove box, installing the glove box on a ball mill for fixing and screwing, wherein the rotating speed of the ball mill is 380-450rpm/min, the single ball milling time is 0.9-1.1 hours, the interval is 10-20 minutes, the repetition times are 11-13 times, and the total ball milling time is 12-13 hours, thus obtaining the ternary Zn formed by Zn, Ge and P elementsxSiyPzA compound is provided.
According to the invention, argon is used as inert atmosphere, air in the stainless steel tank is removed, and the tank is filled with Ar gas in inert atmosphere, so that raw materials are prevented from being oxidized in the subsequent ball milling process; the oxygen content of water in the glove box is less than 1 ppm; the ball-material ratio of the stainless steel beads to the powder material in the stainless steel ball-milling tank is 20:1, ensuring that the ball milling process has enough collision shearing force and providing enough energy for the reaction.
Further, in the step (1), z is 1-7, x is 0.5-1, and y is equal to z-x, wherein the molar ratio of zinc powder, germanium powder and red phosphorus is preferably 1:1:2, so that the raw materials are fully reacted.
Further, in the step (2), the rotation speed of the ball mill is 400rpm/min, the single ball milling time is 1 hour, the interval is 15 minutes, the repetition times are 12 times, and the total ball milling time is 12 hours.
Further, the Zn isxGeyPzThe compound is ZnGeP2、ZnGe3P4、ZnGe6P7、ZnGe2P3、ZnGe4P5、ZnGe5P6、Zn0.143Ge0.857P、Zn0.167Ge0.833P、Zn0.2Ge0.8P、Zn0.25Ge0.75P、Zn0.333Ge0.667P、Zn0.5Ge0.5P is one of the groups.
Further, the germanium powder is replaced by silicon powder to prepare ternary ZnxSiyPzA compound is provided.
Further, silicon powder is replaced by germanium powder, copper powder is replaced by zinc powder, and the ternary alloy is preparedElement CuxSiyPzA compound is provided.
Further, the preparation method of the lithium ion battery multi-element alloy negative electrode material further comprises the following steps:
will be ternary ZnxSiyPz、ZnxSiyPzOr CuxSiyPzAnd (3) respectively mixing the compound with the carbon material according to the mass ratio of 5-7: 2-4, adding the mixture into a stainless steel ball milling tank, setting the rotation speed of the ball mill to be 380-450rpm/min, wherein the single ball milling time is 0.9-1.1 hours, the time interval is 10-20 minutes, the repetition times are 9-11 times, and the total ball milling time is 9-11 hours, thus obtaining the composite material consisting of the compound and the carbon material.
Further, in the step (2), the rotation speed of the ball mill is set to be 400rpm/min, the single ball milling time is 1 hour, the interval is 15 minutes, the repetition times are 10 times, and the total ball milling time is 10 hours. Further, the carbon material is conductive carbon black C45SuperP, natural graphite, acetylene black, Ketjen black, and activated carbon. The series of carbon material conductive components have good mechanical flexibility, high conductivity and chemical stability, and can promote the rapid migration and conduction of electrons so as to improve the cycle stability and electrochemical performance of the active material.
A lithium ion battery multi-element alloy cathode material is prepared by the preparation method of any one of the lithium ion battery multi-element alloy cathode materials.
Compared with the prior art, the invention has the beneficial effects that:
the ternary Zn is prepared by adopting the preparation method of the invention under the conditions of specific molar ratio and specific ball milling processxGe1- xP、ZnxSi1-xP、CuxSi1-xP and Zn thereofxGe1-xP/C、ZnxSi1-xP/C、CuxSi1-xThe P/C and other carbon composite materials reduce or even avoid the use of Ge, are friendly to Ge resources, and effectively reduce the cost, and the material prepared on the basis also has the advantages of large specific discharge capacity, high first coulombic efficiency, good reversibility, excellent electrochemical performance and the like.The ball milling process conditions of the invention provide better collision shearing force, enough reaction time and reaction energy for the reaction, ensure the continuous reaction and reduce the introduction of impurities, the higher rotating speed or the overlong ball milling time can consume extra energy and time to increase the cost, and extra scrap iron impurities can be introduced, and the effect is worse. A certain ball milling interval time is set to provide buffering time for the forward-reverse switching of the instrument, and the instrument is protected to a certain extent. In addition, the invention utilizes the mechanical flexibility, high conductivity and chemical stability of the carbon material to effectively improve the cycle stability and rate capability of the cathode active material, and the ball milling process for mixing the ternary compound and the carbon material ensures that the ternary compound and the carbon material are in an atomic-level high composite state, rather than a simple physical mixing process.
In general, the lithium ion battery multi-element alloy cathode material and the preparation method thereof provided by the invention have the advantages of simple process, low cost, capability of batch synthesis preparation and easiness in large-scale production and synthesis. Compared with the existing like products, the invention also has the following advantages:
compared with the traditional binary metal phosphide such as CoPx、GePx、MnPxAnd the like (Co is toxic, and Co, Mn and Ge are expensive), the ternary metal phosphide is synthesized by replacing and partially replacing Zn, Cu and Si simple substances with rich resources and low price, the cost of the phosphide is greatly reduced on the basis of keeping the same electrochemical performance level, and the preparation, the popularization and the use in a large scale are easy.
Compared with a binary alloy type cathode material, the series Zn-Ge-P, Zn-Si-P, Cu-Si-P multi-element alloy cathode provided by the invention can promote the rapid conduction of electrons, buffer the volume expansion in the lithiation process and maintain the integrity of the electrode appearance by utilizing the 'synergistic effect' among the components, thereby improving the cycling stability of the electrode.
The series Zn-Ge-P, Zn-Si-P, Cu-Si-P and other multi-element alloys provided by the invention have no definite stoichiometric ratio among elements, have adjustable element components, arbitrarily adjustable proportion and wider solid solution range, provide great flexibility for adjusting the conductivity and reversible capacity of the electrode slice and are incomparable with other compounds with fixed stoichiometric ratio.
Compared with the traditional commercialized graphite cathode material (the theoretical capacity is only 372mAh/g), the series of Zn-Ge-P, Zn-Si-P, Cu-Si-P alloys synthesized by the invention are multi-active materials, wherein Zn, P, Ge and Si elements can be subjected to alloying reaction with Li to generate LiZn and LixGe、Li3P and LixSi, contributing to a larger discharge capacity: (>1000mAh/g)。
The preparation method adopts a mechanical ball milling method to synthesize and prepare the multi-element alloy cathode material, can be carried out at normal temperature and normal pressure, has less energy consumption, high yield and high product purity, saves the cost, and is easy for large-scale popularization and preparation.
When the traditional metal phosphide is used as the negative electrode material of the lithium ion battery, the problems of low electronic conductivity, volume expansion of active substance particles and pulverization and shedding can be faced in the lithiation process, thereby causing the failure of the material and the rapid attenuation of the capacity. According to the invention, the conductive carbon material and the active material are compounded by adopting a mechanical ball milling method to prepare the composite material of the multi-element alloy cathode and the carbon material, the electron transmission of the active material in the lithiation process can be promoted by utilizing the high conductivity, the mechanical flexibility and the chemical stability of the carbon material, and the volume expansion is inhibited, so that the completeness of the appearance is maintained, the cycle stability of the battery is greatly improved, and the service life of the battery is greatly prolonged. The carbon compounding method can also be applied to improving the cycle life and the electrochemical performance of other alloy type cathode materials.
Drawings
FIG. 1 ZnGeP under different ball milling time2X-ray diffraction pattern of (a).
FIG. 2.ZnGeP2Schematic of the crystal structure of (a).
FIG. 3 Synthesis of product ZnGeP of example 12X-ray diffraction pattern of (a).
FIG. 4 Synthesis of product ZnSiP in example 12X-ray diffraction pattern of (a).
FIG. 5 Synthesis of product ZnGeP of example 12Scanning electron microscope image ofSpectrum and corresponding element distribution spectrum.
FIG. 6 Synthesis of product ZnGeP of example 12(a)、ZnGe3P4(b)、ZnGe6P7(c) The charge and discharge curve of (1).
FIG. 7 Synthesis of product ZnGe of real time example 13P4And ZnGe3P4Electrochemical cycle performance of the/C composite material.
Detailed Description
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention.
The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified.
The materials, reagents and the like used in the examples of the present invention can be obtained commercially without specific description.
Example 1
The preparation method of the synthetic multi-element alloy negative electrode material mainly comprises the following steps:
weighing and proportioning zinc powder, germanium powder (99.999%) and red phosphorus (99.9%) according to a molar ratio of 1:1:2, adding the zinc powder, the germanium powder and the red phosphorus into a stainless steel ball milling tank, putting the stainless steel ball milling tank into a glove box (without water and oxygen, and the content of water and oxygen is less than 1ppm) filled with inert atmosphere (Ar gas protection), and sealing and covering the stainless steel tank in the glove box (locking and sealing by using a locking device).
Secondly, taking the stainless steel tank out of the glove box, installing the stainless steel tank on a ball mill for fixing and screwing, setting the rotating speed of the ball mill to be 400rpm/min, setting the single ball milling time to be 1 hour, setting the interval to be 15 minutes, repeating the times for 12 times, namely, the total ball milling time is 12 hours, and obtaining the ternary ZnGeP formed by Zn, Ge and P elements2A compound is provided.
Further, Zn can be prepared by replacing the germanium powder with silicon powderxSiyPzMulticomponent alloy materials, e.g. ZnSiP2A compound is provided.
Further, the germanium powder is replaced by silicon powder, and the zinc powder is replaced by copper powder, so that Cu can be preparedxSiyPzMulticomponent alloy materials, e.g. CuSiP2A compound is provided.
Furthermore, Zn with different proportion compositions can be prepared by adjusting the molar ratio of the zinc powder, the germanium powder and the red phosphorusxGeyPzMulticomponent alloy material comprising ZnGe3P4、ZnGe6P7、ZnGe2P3、ZnGe4P5、ZnGe5P6、Zn0.143Ge0.857P、Zn0.167Ge0.833P、Zn0.2Ge0.8P、Zn0.25Ge0.75P、Zn0.333Ge0.667P、Zn0.5Ge0.5P, and the like.
ZnGeP2The crystal structure of (A) is shown in FIG. 2 and is a cubic crystal system structure, F-43m space group, unit cell parameter a is
Volume of
It is worth mentioning that the atomic coordinates occupied by Zn and Ge are the same position, which provides the basic condition for synthesizing the series Zn-Ge-P, Zn-Si-P, Cu-Si-P ternary alloy for the substitution of different elements and also provides the Zn with different proportionsxGeyPzProvides a theoretical basis for the synthesis of (A). Among them, Zn, Ge, Si, P and other components all have lithium storage activity, and can contribute additional capacity through multi-electron alloying reaction, so that the series Zn-Ge-P, Zn-Si-P all have higher reaction activity and larger discharge capacity.
As shown in FIG. 3, XRD diffraction peak pattern and ZnGeP2The standard PDF Card (JCPDS Card No.50-1210) is matched, no redundant diffraction peak exists, and the reaction raw materials are proved to have completely reacted to generate ZnGeP2The existence of Zn simple substance, Ge simple substance and P simple substance is avoided, and the synthesized product has higher yield and purity.
As shown in FIG. 4, and ZnGeP2Similarly, synthetic ZnSiP2XRD diffraction peak pattern (figure 4) and ZnGeP2Matched with the standard PDF Card (JCPDS Card No.50-1210),no redundant diffraction peak exists, and the fact that all reaction raw materials are completely reacted to generate ZnSiP is proved2The method has the advantages of no existence of Si simple substance, Ge simple substance and P simple substance, and higher yield and purity. Furthermore, ZnSiP2And ZnGeP2The alloy has the same diffraction pattern, shows that the two have similar crystal structures and physicochemical properties, and is a substitutional solid solution alloy.
As shown in FIG. 5, for ZnGeP2The morphology characterization is carried out, and ZnGeP can be seen from a scanning electron microscope image (figure 5)2The powder is composed of secondary particles formed by agglomerating primary nano particles into micron-sized particles, the diameters of the particles are different from hundreds of nanometers to microns, and the surface appearance and the shape of the particles are irregular. The elements are analyzed, and the EDS images show that the Zn, Ge and P elements present high composition at an atomic level instead of simple physical mixing, which indicates that the raw materials are completely reacted.
As shown in FIG. 6, electrochemical performance test is carried out on the series synthesized Zn-Ge-P, Zn-Si-P, Cu-Si-P multi-element alloy cathode material, and ZnGeP is used2For example, as shown in fig. 6, a series of Zn-Ge-P ternary alloy materials with different ratios all exhibit higher reactivity, larger discharge capacity, higher first coulombic efficiency and good cycle stability.
The theoretical capacity, the actual discharge capacity, the charge capacity, the first coulombic efficiency and the discharge platform are shown in the following table 1:
TABLE 1 comparison of electrochemical Performance data for Zn-Ge-P in different ratios
The first discharge capacities of the series Zn-Ge-P ternary alloy materials are 1516mAh/g, 1711mAh/g and 1802mAh/g respectively, which are very close to the theoretical capacity and have high reaction activity. At the same time, ZnGeP2、ZnGe3P4And ZnGe6P7The first coulombic efficiencies of the high-efficiency energy-saving power supply respectively reach 86%, 88% and 90%, and the high reversibility reaches the quotientThe level of commercial graphite negative electrodes, without the need for a prelithiation step, can be applied directly in full cell testing. More particularly, the discharge platform of the series Zn-Ge-P is about 0.5V, so that the separation of lithium dendrites on the surface of graphite can be avoided, and the high-voltage platform and high-energy density output of the full battery can be well ensured. Therefore, the novel low-cost and large-capacity multi-element alloy negative electrode material has wide application prospect.
Example 2
The preparation method of the carbon composite material of the multi-component compound mainly comprises the following steps:
the ternary ZnGeP prepared in example 12、ZnSiP2、CuSiP2The compound is respectively mixed with carbon material conductive carbon black C45Weighing according to the mass ratio of 7:2, adding the materials into a stainless steel ball milling tank, setting the ball-material ratio of stainless steel beads to powder materials to be 20:1, setting the rotating speed of the ball mill to be 400rpm/min, carrying out ball milling for 1 hour each time at intervals of 15 minutes for 10 times, namely carrying out ball milling for 10 hours in total, thus obtaining the ZnGeP composite powder2Compound, ZnSiP2、CuSiP2ZnGeP respectively combined with carbon material2a/C composite material, ZnSiP2/C composite material and CuSiP2a/C composite material.
The ternary ZnGeP2、ZnSiP2、CuSiP2Materials and their ZnGeP2The components and the formula of the/C composite material are as follows:
TABLE 2 ZnGeP2Materials and their ZnGeP2Components and formula of/C composite material
TABLE 3 ZnSiP2Material and ZnSiP thereof2Components and formula of/C composite material
TABLE 4 CuSiP2Material and method for producing the sameCuSiP2Components and formula of/C composite material
Further, ternary ZnGeP2The mass ratio of the compound to the carbon material can be adjusted to 6:3 or 5: 4.
Further, carbon material conductive carbon black C45Can be replaced by SuperP, natural graphite, acetylene black, Ketjen black and active carbon.
The invention effectively buffers Zn by utilizing the mechanical flexibility, high conductivity and chemical stability of the carbon materialxGeyPzThe volume of the active particles expands in the lithiation process, so that the shape integrity of the electrode is maintained, the electrochemical cycle stability of the cathode active material is improved, and the ball milling process for mixing the ternary compound and the carbon material ensures that the ternary compound and the carbon material are in an atomic-level high composite state instead of a simple physical mixing process.
TABLE 5 ZnGeP2Materials and their ZnGeP2Comparison of electrochemical Properties of the/C composite
TABLE 6 ZnGe3P4Material and ZnGe thereof3P4Comparison of electrochemical Properties of the/C composite
As shown in FIG. 7, tables 5 and 6, Zn was included in series at different ratiosxGeyPzZn after efficient recombination with carbon material (SuperP)xGeyPzboth/C exhibited good capacity retention and electrochemical cycling stability. With ZnGeP2For example, phase-pure ZnGeP2The first-cycle discharge capacity of the electrode material is 1337.4mAh/g, and the electrode material is cycled for 100 timesAfter the ring, the reversible discharge capacity decayed to 239.8mAh/g, and the capacity retention rate was only 17.93%. In contrast, ZnGeP after complexing with carbon materials2The first-turn discharge capacity of the/C composite electrode material is 1385.2mAh/g, after 100 cycles, the reversible discharge capacity still has 546.5mAh/g, the capacity retention rate is 39.45%, and the cycle life of the battery is greatly prolonged.
For another example, in Table 6, the phase pure ZnGe3P4The discharge capacity of the electrode material at the first circle is 1766.7mAh/g, after 100 cycles, the reversible discharge capacity is attenuated to 246.5mAh/g, and the capacity retention rate is only 14.9%. In contrast, after complexing with carbon materials, ZnGe3P4The first-turn discharge capacity of the/C composite electrode material is 1702mAh/g, the reversible discharge capacity is still 897.5mAh/g after 100 cycles, the capacity retention rate is 52.73%, and the electrochemical cycling stability is effectively improved.
Example 3
Based on example 1, the total ball milling time of 12 hours was adjusted to 1 hour, 3 hours, 5 hours, and 8 hours. ZnGeP under different ball milling time2The X-ray diffraction pattern of (A) is shown in FIG. 1. It can be seen that pure phase is obtained when the total ball milling time is 12 h. When the total ball milling time is less than or equal to 8h, Ge impurities are left in the synthesized product, and when the total ball milling time is only 1h, more Ge and Zn impurities are left in the synthesized product.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a lithium ion battery multi-element alloy cathode material is characterized by comprising the following steps:
(1) zinc powder, germanium powder and red phosphorus are mixed according to a molar ratio x: y: z, mixing, adding y to z-x into a stainless steel ball milling tank, putting the stainless steel tank into a glove box filled with inert atmosphere, and sealing and tightly covering the stainless steel tank in the glove box;
(2) taking out the stainless steel potThe glove box is taken out and installed on the ball mill for fixing and screwing, the rotating speed of the ball mill is 380-450rpm/min, the single ball milling time is 0.9-1.1 hours, the time interval is 10-20 minutes, the repeating times are 11-13 times, and the total ball milling time is 12-13 hours, thus obtaining the ternary Zn formed by Zn, Ge and P elementsxGeyPzA compound is provided.
2. The method for preparing the multi-element alloy negative electrode material of the lithium ion battery according to claim 1, wherein in the step (1), z is 1 to 7, x is 0.5 to 1, and y is z-x.
3. The preparation method of the lithium ion battery multi-element alloy negative electrode material as claimed in claim 1, wherein in the step (2), the rotation speed of the ball mill is 400rpm/min, the single ball milling time is 1 hour, the interval is 15 minutes, the number of times of the ball milling is repeated for 12 times, and the total ball milling time is 12 hours.
4. The preparation method of the lithium ion battery multi-element alloy negative electrode material of claim 1, wherein the Zn isxGeyPzThe compound is ZnGeP2、ZnGe3P4、ZnGe6P7、ZnGe2P3、ZnGe4P5、ZnGe5P6、Zn0.143Ge0.857P、Zn0.167Ge0.833P、Zn0.2Ge0.8P、Zn0.25Ge0.75P、Zn0.333Ge0.667P、Zn0.5Ge0.5P is one of the groups.
5. The preparation method of the lithium ion battery multi-element alloy negative electrode material according to claim 1, characterized by further comprising the following steps: will be ternary ZnxGeyPzThe mass ratio of the compound to the carbon material is 5-7: 2-4, adding the mixture into a stainless steel ball milling tank, setting the rotating speed of the ball mill to be 380-450rpm/min, setting the single ball milling time to be 0.9-1.1 hours, the time interval to be 10-20 minutes, repeating the time for 9-11 times,the total ball milling time is 9 to 11 hours, and Zn is obtainedxGeyPzZn composed of compound and carbon materialxGeyPza/C composite material.
6. The preparation method of the lithium ion battery multi-element alloy cathode material according to claim 5, wherein in the step (2), the rotation speed of the ball mill is set to 400rpm/min, the single ball milling time is 1 hour, the interval is 15 minutes, the repetition times are 10 times, and the total ball milling time is 10 hours.
7. The preparation method of the lithium ion battery multi-element alloy negative electrode material as claimed in claim 5, wherein the carbon material is conductive carbon black C45SuperP, natural graphite, acetylene black, Ketjen black, and activated carbon.
8. The preparation method of the lithium ion battery multi-element alloy cathode material according to claim 1 or 5, wherein the germanium powder is replaced by silicon powder to prepare ternary ZnxSiyPzA compound is provided.
9. The preparation method of the lithium ion battery multi-element alloy cathode material as claimed in claim 1 or 5, wherein the germanium powder is replaced by silicon powder, and the zinc powder is replaced by copper powder to prepare ternary CuxSiyPzA compound is provided.
10. A lithium ion battery multi-element alloy negative electrode material, which is characterized by being prepared by the preparation method of the lithium ion battery multi-element alloy negative electrode material of any one of claims 1 to 9.
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