CN112993201A - Lithium ion conductor compounded lithium alloy negative electrode material and preparation method and application thereof - Google Patents

Lithium ion conductor compounded lithium alloy negative electrode material and preparation method and application thereof Download PDF

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CN112993201A
CN112993201A CN202110154459.7A CN202110154459A CN112993201A CN 112993201 A CN112993201 A CN 112993201A CN 202110154459 A CN202110154459 A CN 202110154459A CN 112993201 A CN112993201 A CN 112993201A
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lithium
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electrode material
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CN112993201B (en
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朱昌宝
彭琨尧
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Sun Yat Sen University
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    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract

The invention discloses a lithium ion conductor compounded lithium alloy negative electrode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing polyanion compound nanoparticles with lithium metal uniformly, heating the mixture to a molten state under an inert atmosphere, and reacting for 1-48 h to obtain a lithium alloy cathode material compounded by a lithium ion conductor; the mass ratio of the lithium metal to the polyanionic compound nanoparticles is 1: (0.1 to 1). Compared with the traditional pure lithium cathode, the lithium alloy cathode material has high rate performance and good cycle performance, and can be applied to energy storage systems such as lithium metal batteries, solid-state batteries and the like.

Description

Lithium ion conductor compounded lithium alloy negative electrode material and preparation method and application thereof
Technical Field
The invention relates to the field of lithium metal negative electrode materials, in particular to a lithium alloy negative electrode material compounded by a lithium ion conductor and a preparation method and application thereof.
Background
Lithium ion batteries currently occupy a great market share in the fields of consumer electronics, electric vehicles and the like. The negative electrode material of the lithium ion battery is mainly graphite (372mAh/g) and a silicon-carbon composite material (1500 mAh/g) at present, and the specific capacity of the negative electrode material is lower than that of a lithium metal negative electrode (theoretical value 3860 mAh/g). However, lithium metal itself has high chemical activity and easily generates lithium dendrite during deposition/dissolution of lithium metal, thereby causing side reaction of lithium metal with electrolyte and the problem of dendrite penetration short circuit. These problems make commercialization of lithium metal negative electrodes difficult. At present, the research on the inhibition of the growth of lithium metal dendrites mainly comprises three ideas: 1. the porous conductive current collector is used as a substrate of the lithium metal negative electrode, so that the local current density of the lithium metal negative electrode during working is reduced, and the growth of dendrites is inhibited; 2. a stable and uniform solid-electrolyte interface film (SEI) is constructed, so that lithium ions are uniformly distributed on an electrode-electrolyte interface, and the growth of dendrites is avoided; 3. solid electrolytes are used to isolate dendrites by virtue of their uniformity and excellent mechanical strength.
As disclosed in chinese patent publication No. CN110120502A, published as 2019, 08 and 13, a lithium metal alloy negative electrode material is disclosed, which includes a lithium alloy as a framework and metal lithium filled in the framework, and the negative electrode material uses a porous current collector as a negative electrode substrate when preparing a negative electrode of a lithium ion battery. The scheme that the porous current collector is used as the negative electrode substrate can effectively reduce the local current density of lithium metal work and improve the rate performance of the electrode, but the porous current collector needs to be fully soaked by electrolyte and is difficult to apply to a solid electrolyte system. The latter two schemes inhibit the growth and piercing of lithium dendrites by improving the uniformity of lithium metal interfaces, but the rate performance of the lithium metal negative electrode is not improved, the volume change is large in the lithium metal charge-discharge process, and the problem that the metal negative electrode is peeled from SEI (solid electrolyte interface) when the lithium metal works at a high charge-discharge depth is solved. Therefore, it is urgently needed to provide a negative electrode material which has a high specific capacity, is not easy to generate lithium dendrite, and has excellent rate performance, good cycle performance and interface stability.
Disclosure of Invention
The invention aims to overcome the problems of lithium dendrite growth caused by uneven deposition of lithium metal during deposition-dissolution of a lithium metal negative electrode and over-high over-potential during charge and discharge due to unstable lithium-electrolyte interface, and provides a preparation method of a lithium alloy negative electrode material compounded by a lithium ion conductor. The lithium ion conductor-lithium alloy composite negative electrode material prepared by the invention has excellent rate performance, good cycle performance and interface stability.
The invention further aims to provide the lithium alloy negative electrode material prepared by the preparation method.
The invention also aims to provide application of the lithium alloy negative electrode material.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a lithium ion conductor compounded lithium alloy negative electrode material comprises the following steps:
mixing polyanion compound nanoparticles with lithium metal uniformly, heating the mixture to a molten state under an inert atmosphere, and reacting for 1-48 h to obtain a lithium alloy cathode material compounded by a lithium ion conductor; the mass ratio of the lithium metal to the polyanionic compound nanoparticles is 1: (0.1 to 1).
According to the invention, polyanionic compound nanoparticles are mixed with lithium metal, and are further pulverized by utilizing the conversion reaction of the polyanionic compound nanoparticles and molten lithium metal, and the lithium alloy negative electrode material compounded by the lithium ion conductor and formed by uniformly mixing a lithium alloy and a lithium ion conductor is generated.
The lithium ion conductor is uniformly doped into the lithium alloy through a melting method, so that the ionic conductivity in the lithium alloy composite electrode is effectively improved, lithium ions are simultaneously subjected to lithium deposition/dissolution on the surface and in the composite electrode in the charging and discharging processes, and the rate performance is superior to that of lithium metal. Such lithium deposition/elution performed by the entire electrode body phase also alleviates the volume change of the lithium negative electrode at the lithium metal-electrolyte interface, and improves the interface stability of the lithium negative electrode.
In the invention, the mass ratio of the lithium metal to the polyanionic compound nanoparticles affects the specific capacity of the lithium alloy negative electrode material compounded by the lithium ion conductor, and when the polyanionic compound is more, the specific capacity is reduced. Preferably, the mass ratio of the lithium metal to the polyanionic compound nanoparticles is 1: (0.1-0.6).
Preferably, the reaction temperature is 180-350 ℃, and the reaction time is 1-12 h.
Preferably, the inert atmosphere is one or both of argon and helium.
The molecular general formula of the polyanionic compound is LixMy(XOn)zWherein x can be any natural number from 0 to 4, and y, n and z are any natural number from 1 to 4; m is selected from one of the metal elements capable of forming an alloy with lithium metal, such as Ag, Mg, Zn, Al, and X is selected from one of the non-metal elements such as S, P, Si, C, N, and LiAgSO4，LiMgPO4，LiZnPO4，LiAlSiO4，AlPO4And the like.
The polyanionic compound nanoparticles can be prepared by conventional preparation methods in the field, such as a solvothermal method, a hydrothermal method, a solid-phase calcination method and the like. Preferably, the method for preparing the polyanionic compound nanoparticles comprises the steps of:
the polyanion compound nanoparticles are prepared by using a lithium source, a metal salt and an oxoammonium salt as precursors or only using the metal salt and the oxoammonium salt.
Lithium sources, metal salts, and oxysalts, which are conventional in the art, can be used in the preparation of the polyanionic compound nanoparticles.
Preferably, the lithium source is one or more of lithium acetate, lithium chloride, lithium oxalate, lithium alginate, lithium carbonate, lithium nitrate, lithium oxide and lithium hydroxide.
Preferably, the metal salt is at least one salt compound of a metal element capable of forming an alloy with lithium metal.
Specifically, the metal salt is one or more of magnesium acetate, zinc acetate, silver acetate, aluminum acetate, zinc nitrate, silver nitrate, aluminum nitrate and magnesium nitrate.
Preferably, the oxoacid ammonium saltSelected from anions of SO4 2-、PO4 3-、SiO4 4-、CO3 2-And NO3 -At least one ammonium salt compound.
Specifically, the ammonium salt of the oxoacid is one or more of ammonium sulfate, ammonium bisulfate, ammonium bicarbonate, ammonium carbonate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate.
Preferably, the method for uniformly mixing the polyanionic compound nanoparticles with the lithium metal is one or more of a roll method, a milling mixing method, a ball milling method, and a melt mixing method.
A lithium ion conductor compounded lithium alloy negative electrode material is obtained by the preparation method.
The lithium alloy cathode material disclosed by the invention has excellent rate performance, good cycle stability and interface stability, meets the performance requirements of the field of lithium metal batteries and solid-state batteries on the cathode material, and can be used in the field of lithium metal batteries and solid-state batteries. Therefore, the application of the lithium alloy negative electrode material in lithium metal batteries and solid-state batteries also should be within the protection scope of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
the lithium alloy negative electrode material compounded by the lithium ion conductor is prepared by heating the polyanionic compound and the lithium metal to a molten state, has excellent rate performance, good cycle performance and interface stability, can relieve the negative effects of cycle performance reduction, high impedance change and the like caused by volume change of a lithium metal negative electrode and an electrolyte interface, and has wide application prospect in a lithium negative electrode end of a lithium metal battery and an all-solid-state battery.
Drawings
Fig. 1 is an X-ray powder diffraction pattern of the lithium alloy negative electrode material prepared in example 6.
Fig. 2 is a diagram showing the electrochemical specific capacity of the lithium alloy negative electrode material prepared in example 6.
Fig. 3 is a graph of rate performance of the lithium alloy negative electrode material prepared in example 6 and lithium metal.
FIG. 4 shows that the lithium alloy negative electrode material prepared in example 6 and lithium metal are both 1mA/cm at 50 times2SEM image of the metal surface morphology after charging and discharging 50 times at the current density of (a).
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
Example 1
A preparation method of polyanionic compound lithium magnesium phosphate nano-particles comprises the following steps:
284.5mg of magnesium acetate, 230mg of ammonium dihydrogen phosphate and 132mg of lithium acetate were dissolved in a mixed solvent of 25mL of tetraethylene glycol and 25mL of oleylamine. The solution is placed in a round-bottom flask with an air condensation reflux device and heated until the solvent is refluxed (about 270 ℃ C. and 320 ℃ C.) for 12 hours, and then the heating is stopped to naturally cool the solution, so as to obtain a nano-particle suspension of polyanionic compound magnesium lithium phosphate. And (3) carrying out centrifugal separation on the suspension, respectively carrying out centrifugal cleaning for 3 times by using ethanol and acetone to remove the organic solvent with high boiling point, and carrying out vacuum drying for 8h at the temperature of 45 ℃ to obtain polyanionic compound magnesium lithium phosphate nano particles.
Example 2
This example is a second example of the present invention, and is different from example 1 in that silver acetate is used as a metal salt, ammonium sulfate is used as an ammonium oxoacid salt, and lithium acetate is used as a lithium source to prepare polyanionic compound silver lithium sulfate nanoparticles.
Example 3
This example is a third example of the present invention, and is different from example 1 in that zinc acetate is used as a metal salt, ammonium dihydrogen phosphate is used as an ammonium salt of an oxoacid, and lithium acetate is used as a lithium source to prepare polyanionic compound lithium zinc phosphate nanoparticles.
Example 4
This example is a fourth example of the present invention, and is different from example 1 in that zinc acetate is used as a metal salt and ammonium dihydrogen phosphate is used as an ammonium salt of an oxoacid to prepare polyanionic compound zinc phosphate nanoparticles.
Example 5
This example is a fifth example of the present invention, and is different from example 1 in that polyanionic compound aluminum phosphate nanoparticles are prepared by using aluminum acetate as a metal salt and ammonium dihydrogen phosphate as an oxoacid ammonium salt.
Example 6
A preparation method of a lithium ion conductor compounded lithium alloy negative electrode material comprises the following steps:
dispersing magnesium lithium phosphate powder with the mass of 20% of that of lithium metal on the surface of a lithium sheet, rolling by using a roller to adhere the powder on the surface of the lithium metal, and repeatedly mixing the powder and the lithium metal uniformly. Or stirring and mixing magnesium lithium phosphate powder with the mass of 20% of lithium metal with lithium metal powder to uniformly mix the magnesium lithium phosphate powder and the lithium metal powder, and grinding and compacting the mixed powder into a sheet or a block by using a mortar; and (3) placing the uniformly mixed precursor material in a stainless steel or nickel container under an argon atmosphere, heating to 230 ℃ to melt the lithium metal mixture, maintaining the temperature for 1h, and naturally cooling to obtain the lithium-ion conductor composite lithium alloy cathode material.
Example 7
This example is a seventh example of the present invention, and is different from example 6 in that the mass ratio of lithium metal to magnesium lithium phosphate in this example is 1: 0.1.
example 8
This example is an eighth example of the present invention, and is different from example 6 in that the mass ratio of lithium metal to magnesium lithium phosphate in this example is 1: 0.4.
example 9
This example is a ninth example of the present invention, and is different from example 6 in that the mass ratio of lithium metal to magnesium lithium phosphate in this example is 1: 0.6.
example 10
This example is a tenth example of the present invention, and is different from example 6 in that the mass ratio of lithium metal to magnesium lithium phosphate in this example is 1: 1.
example 11
This example is an eleventh example of the present invention, and is different from example 6 in that the polyanionic compound in this example is silver lithium sulfate, the heating reaction temperature in this example is 350 ℃, and the reaction time is 1 hour.
Example 12
This example is a twelfth example of the present invention, which is different from example 6 in that the polyanionic compound in this example is lithium zinc phosphate, and the heating reaction time in this example is 3 hours.
Example 13
This example is a thirteenth example of the present invention, which is different from example 6 in that the polyanionic compound in this example is zinc phosphate, and the heating reaction time in this example is 12 hours.
Example 14
This example is a fourteenth example of the present invention, which is different from example 6 in that the polyanionic compound in this example is aluminum phosphate, and the heating reaction temperature in this example is 180 ℃ and the reaction time is 48 hours.
Characterization of the test
The lithium-ion conductor-compounded lithium alloy negative electrode materials of examples 6 to 14 were rolled and cut into lithium sheets with a diameter of 12mm and a mass of 12 to 15mg, and the lithium sheets were used as electrodes with a concentration of 1mol/L of LiPF6The solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC)/Ethyl Methyl Carbonate (EMC) mixed solvent is used as electrolyte, celgard polypropylene is used as a diaphragm, a button type symmetrical battery is assembled in a glove box under argon atmosphere, and the battery is placed still for 6 hours and then subjected to charge and discharge tests.
Fig. 1 is an X-ray powder diffraction pattern of a lithium alloy negative electrode material in which a lithium ion conductor described in example 6 is compounded. Fig. 2 is a graph of electrochemical specific capacity of the lithium alloy negative electrode material compounded by the lithium ion conductor described in example 6, and it can be seen from the graph that the specific capacity of the lithium alloy negative electrode material compounded by the lithium ion conductor generated by the reaction of the lithium metal and the polyanion type compound is 3025mAh/g, which is 78% of the theoretical value (3860mAh/g) of the pure lithium metal. Specific capacities of the lithium alloy negative electrode materials of examples 7 to 14, which were formed by compounding the lithium ion conductors, are shown in table 1.
Fig. 3 is a graph showing rate capability of a lithium alloy negative electrode material compounded with a lithium ion conductor and lithium metal in example 6. As shown in fig. 3, the lithium alloy negative electrode material compounded by the lithium ion conductor shows a lower overpotential at the same current density compared with pure lithium metal, which indicates that the lithium alloy negative electrode material has a superior rate capability. The overpotential of the lithium alloy negative electrode material in which the lithium ion conductor is compounded in examples 7 to 14 is substantially the same as that in example 6.
TABLE 1
Specific capacity (mAh/g)
Example 7 3470
Example 8 2635
Example 9 2252
Example 10 1715
Example 11 3008
Example 12 2996
Example 13 2983
Example 14 3030
FIG. 4 shows that the lithium alloy negative electrode material and the common lithium metal in example 6 are both 1mA/cm at 50 times2The SEM images of the metal surface morphology after 50 charging and discharging times under the current density of (1) are SEM images of the metal surface before the cycle test of the lithium alloy negative electrode material, 2 is SEM image of the metal surface after the cycle test of the lithium alloy negative electrode material, 3 is SEM image of the surface before the cycle test of the general lithium metal, and 4 is SEM image of the surface after the cycle test of the general lithium metal. As shown in fig. 4 1 and 2, after charging and discharging for 50 times, the surface of the lithium alloy negative electrode material compounded by the lithium ion conductor is still relatively flat; compared with the prior art, under the same condition, a large number of dendrites and cracks grow on the surface of the lithium metal, which illustrates the problem of lithium dendrite growth caused by uneven deposition of the lithium metal during deposition-dissolution of the lithium metal cathode, and can be obviously improved after alloying and doping of an ion conductor. The lithium alloy negative electrode material described in examples 7 to 14 was 1mA/cm at 50 times2The SEM image of the metal surface appearance after charging and discharging for 50 times under the current density is basically consistent with that of the metal surface appearance in the embodiment 1, the surface is relatively flat, and no dendrite or crack exists.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. A preparation method of a lithium ion conductor compounded lithium alloy negative electrode material is characterized by comprising the following steps:
mixing polyanion compound nanoparticles with lithium metal uniformly, heating the mixture to a molten state under an inert atmosphere, and reacting for 1-48 h to obtain a lithium alloy cathode material compounded by a lithium ion conductor; the mass ratio of the lithium metal to the polyanionic compound nanoparticles is 1: (0.1 to 1).
2. The method for preparing a lithium alloy negative electrode material compounded by a lithium ion conductor according to claim 1, wherein the mass ratio of the lithium metal to the polyanionic compound nanoparticles is 1: (0.1-0.6).
3. The preparation method of the lithium ion conductor compounded lithium alloy negative electrode material as claimed in claim 1, wherein the reaction temperature is 180-350 ℃ and the reaction time is 1-12 h.
4. The method for preparing a lithium-ion conductor-composited lithium alloy negative electrode material as claimed in claim 1, wherein the inert atmosphere is one or both of argon and helium.
5. The method for preparing a lithium alloy negative electrode material compounded by a lithium ion conductor according to claim 1, wherein the method for preparing the polyanion compound nanoparticles comprises the following steps:
the polyanion compound nanoparticles are prepared by using a lithium source, a metal salt and an oxoammonium salt as precursors or only using the metal salt and the oxoammonium salt.
6. The method for preparing a lithium alloy negative electrode material compounded by a lithium ion conductor according to claim 5, wherein the lithium source is one or more of lithium acetate, lithium chloride, lithium oxalate, lithium alginate, lithium carbonate, lithium nitrate, lithium oxide and lithium hydroxide.
7. The method for producing a lithium alloy negative electrode material in which a lithium ion conductor is combined as claimed in claim 5, wherein the metal salt is at least one salt compound of metal elements capable of forming an alloy with lithium metal.
8. The method for preparing a lithium alloy negative electrode material compounded by a lithium ion conductor according to claim 5, wherein the ammonium salt of an oxoacid is selected from the group consisting of SO as an anion4 2-、PO4 3-、SiO4 4-、CO3 2-And NO3 -At least one ammonium salt compound.
9. A lithium ion conductor compounded lithium alloy negative electrode material is characterized by being prepared by the method of any one of claims 1 to 8.
10. Use of the lithium ion conductor composite lithium alloy negative electrode material according to claim 9 in a lithium metal battery or a solid-state battery.
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CN114050253A (en) * 2021-10-21 2022-02-15 中山大学 Preparation method and application of nano lithium alloy

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