CN112510179B - Battery negative electrode material and preparation method and application thereof - Google Patents

Battery negative electrode material and preparation method and application thereof Download PDF

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CN112510179B
CN112510179B CN202011391593.0A CN202011391593A CN112510179B CN 112510179 B CN112510179 B CN 112510179B CN 202011391593 A CN202011391593 A CN 202011391593A CN 112510179 B CN112510179 B CN 112510179B
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negative electrode
electrode material
source
preparation
battery
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CN112510179A (en
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宫勇吉
翟朋博
陈乾
刘伟
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Beijing zhongruitai New Material Co.,Ltd.
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    • 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
    • H01M4/362—Composites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • 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
    • H01M4/58—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Abstract

The invention relates to the technical field of electrode materials, in particular to a battery cathode material and a preparation method and application thereof. The invention provides a preparation method of a battery cathode material, which comprises the following steps: mixing a soluble gallium source, a soluble indium source, a carbon source, a template agent and water, and freeze-drying to obtain precursor mixed powder; and calcining the precursor mixed powder in a reducing atmosphere to obtain the battery negative electrode material. The battery cathode material prepared by the preparation method provided by the invention enables the liquid metal to be firmly combined with graphene, avoids the agglomeration of the liquid metal, and also fully utilizes the self-healing repair capability of lithium desorption of the liquid metal. Therefore, the catalyst has better cycle stability.

Description

Battery negative electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrode materials, in particular to a battery cathode material and a preparation method and application thereof.
Background
At present, the negative electrode of a commercial lithium ion battery is graphite, and the working principle of the battery is that the intercalation theoretical specific capacity of lithium ions in graphite lattices is 372 mAh/g; with the development of industries such as electric automobiles, the graphite cathode cannot meet the requirement of high capacity. Lithium metal has the lowest electrochemical potential (-3.04Vvs. RHE) and the highest theoretical specific capacity (3860mAh/g), so that the lithium metal becomes the most ideal lithium battery negative electrode material. However, the lithium metal negative electrode has problems of poor deposition uniformity, lithium dendrite growth and the like during use, and the practical application of the lithium metal negative electrode is seriously influenced. The surface modification of the lithium deposition substrate is an effective method for adjusting the deposition uniformity of lithium metal and inhibiting the growth of lithium dendrites. For example, loading metal particles (Au, Ag, and the like) having excellent lithium affinity on the surface of graphene can induce uniform deposition of lithium metal on the surface of a substrate. However, these metals, Au and Ag, have the disadvantages of high cost, large volume change, unstable structure and size, and weak contact with the substrate. How to obtain the metal nano particles which have low cost, excellent lithium affinity, stable structure and firm combination with the substrate and realize the uniform load of the metal nano particles on the surface of the negative electrode is the key for obtaining the lithium metal negative electrode with excellent performance.
In order to solve the problems, a metal nanoparticle capable of realizing self-healing repair in a lithium metal deposition/desorption process is urgently needed to be found, so that the metal nanoparticle is uniformly loaded on a substrate, and the induction effect on the lithium metal deposition behavior in a long-cycle process is realized. The room-temperature liquid metal GaIn can not only realize the recovery of morphology after lithium desorption, but also realize the recovery of performance after damage. However, in the practical use process of the liquid metal GaIn negative electrode, uniform dispersion and adhesion on the surface of the current collector cannot be realized (the wettability between the liquid metal GaIn negative electrode and the current collector is very poor, for example, the contact angle on the surface of the carbon material is close to 180 ℃, liquid particles are easy to agglomerate and become large, and the size is in the micron level), so that the liquid metal GaIn negative electrode cannot be applied to a lithium metal battery.
For example, Yu et al (adv. funct. mater.2018,1804649, DOI:10.1002/adfm.201804649) utilize GaIn liquid metal as a negative electrode material of a lithium ion battery by placing the GaIn liquid metal in an organic solvent, dispersing the GaIn into micron-sized particles using a cell crusher, mixing the GaIn particles with conductive carbon black into a slurry, and coating and collecting the slurry on the surface of a current collector, wherein the size of the liquid metal is in the micron level and cannot reach the nanometer level. Meanwhile, the electrode is applied to a lithium ion battery, and cannot be applied to a lithium metal battery.
Disclosure of Invention
The invention aims to provide a battery negative electrode material, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a battery cathode material, which comprises the following steps:
mixing a soluble gallium source, a soluble indium source, a carbon source, a template agent and water, and freeze-drying to obtain precursor mixed powder;
and calcining the precursor mixed powder in a reducing atmosphere to obtain the battery negative electrode material.
Preferably, the mass ratio of the template agent to the carbon source to the soluble gallium source to the soluble indium source is (10-20): (1-2): (0.2-0.4): (0.05-0.1);
the mass ratio of the carbon source to the water is 1 (60-100).
Preferably, the carbon source is one or more of glucose, citric acid and ammonium citrate.
Preferably, the template agent is one or more of ammonium chloride, sodium chloride and sodium carbonate.
Preferably, the soluble gallium source is GaCl3And/or Ga (NO)3)3；
The soluble indium source is InCl3And/or In (NO)3)3。
Preferably, the temperature of the freeze drying is-50 ℃, the pressure is 1-30 Pa, and the time is 20-48 h.
Preferably, the calcining temperature is 900 ℃, and the heat preservation time is 2-4 h.
The invention also provides a battery cathode material prepared by the preparation method in the technical scheme, which comprises graphene and liquid metal particles loaded on the surface of the graphene;
the liquid metal particles are GaIn.
Preferably, the mass ratio of the GaIn to the graphene is (5-15): 100.
the invention also provides the application of the battery cathode material in the technical scheme in a lithium metal battery or a lithium ion battery.
The invention provides a preparation method of a battery cathode material, which comprises the following steps: mixing a soluble gallium source, a soluble indium source, a carbon source, a template agent and water, and freeze-drying to obtain precursor mixed powder; mixing the precursor mixed powder under a reducing atmosphereAnd calcining to obtain the battery negative electrode material. According to the preparation method, a mode of in-situ high-temperature calcination is adopted, and nanoscale liquid metal particles are generated in situ on the surface of graphene. The liquid metal particles are uniformly loaded on the surface of the graphene. Meanwhile, the liquid metal and the graphene substrate are firmly combined in an in-situ growth mode. The nano-sized liquid metal particles can realize self-healing repair after lithium desorption by utilizing the unique physical properties of the nano-sized liquid metal particles, so that the induction effect on the deposition behavior of lithium metal is kept in the long circulation process, the growth of lithium dendrites is avoided, and the performance of a lithium metal negative electrode is ensured. According to the description of the embodiment, the lithium metal negative electrode prepared by the preparation method is 1mAh/cm2&1mA/cm2The average coulombic efficiency is 99.3 percent under the parameters of (1) and the cycle is 400 circles, and the average coulombic efficiency is 2mAh/cm2&2mA/cm2The average coulombic efficiency was 98.7% with 120 cycles of cycles under the parameters (D).
Drawings
Fig. 1 is an SEM image of a battery anode material prepared in example 1;
FIG. 2 is an SEM image of a battery anode material prepared in example 2;
FIG. 3 is an SEM image of a battery anode material prepared in example 3;
FIG. 4 is a micro-topography of lithium metal of different capacities deposited on the battery negative electrode material prepared in example 1;
FIG. 5 shows the cell negative electrode material obtained in example 2 or a half cell obtained by using the cell negative electrode material obtained in comparative example at 1mAh/cm2&1mA/cm2A cycle performance map under the parameters of (a);
FIG. 6 shows the negative electrode material of the battery prepared in example 2. about.2 mAh/cm of a half-cell prepared from the negative electrode material of the battery2&2mA/cm2Cycle performance plot under the parameters of (1).
Detailed Description
The invention provides a preparation method of a battery cathode material, which comprises the following steps:
mixing a soluble gallium source, a soluble indium source, a carbon source, a template agent and water, and freeze-drying to obtain precursor mixed powder;
and calcining the precursor mixed powder in a reducing atmosphere to obtain the battery negative electrode material.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
The method comprises the steps of mixing a soluble gallium source, a soluble indium source, a carbon source, a template agent and water, and carrying out freeze drying to obtain precursor mixed powder. In the present invention, the soluble gallium source is preferably GaCl3And/or Ga (NO)3)3More preferably GaCl3(ii) a When the soluble gallium source is GaCl3And Ga (NO)3)3In the invention, GaCl is added3And Ga (NO)3)3The proportion of the components is not limited in any way, and the components are mixed according to any proportion. In the present invention, the soluble indium source is InCl3And/or In (NO)3)3More preferably InCl3(ii) a When the soluble indium salt is InCl3And In (NO)3)3Then, the invention is to InCl3And In (NO)3)3The proportion of the components is not limited in any way, and the components are mixed according to any proportion. In the invention, the carbon source is preferably one or more of glucose, citric acid and ammonium citrate, and is more preferably glucose; when the carbon source is more than two of the above specific choices, the invention does not have any special limitation on the proportion of the specific substances, and the specific substances are mixed according to any proportion. In the invention, the template agent is preferably one or more of ammonium chloride, sodium chloride and sodium carbonate, and more preferably ammonium chloride; when the template agent is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion. In the present invention, the water is preferably deionized water.
In the invention, the mass ratio of the template agent to the carbon source to the soluble gallium source to the soluble indium source is preferably (10-20): (1-2): (0.2-0.4): (0.05-0.1), more preferably (12-18): (1.2-1.8): (0.25-0.35): (0.06-0.09), most preferably (14-16): (1.5-1.6): (0.27-0.31): (0.07-0.08). In the invention, the mass ratio of the carbon source to the water is preferably 1 (60-100), more preferably 1: (70-90), most preferably 1: (75-85).
The mixing is not limited in any way, and the soluble gallium source, the soluble indium source, the carbon source and the template agent can be completely dissolved in water by adopting a sequence and a mode which are well known to a person skilled in the art.
In the invention, the freeze drying temperature is preferably-50 ℃, the pressure is preferably 1-30 Pa, more preferably 5-20 Pa, and the time is preferably 20-48 h, more preferably 30-40 h. In the present invention, the freeze-drying process is preferably performed by freezing the mixed solution obtained after the mixing at-50 ℃ to a frozen state, and then placing the frozen mixed solution in a freeze-drying machine to sublimate ice in a vacuum environment, thereby achieving the purpose of drying.
In the invention, the freeze drying can ensure that the metal salt and the grape poplar are uniformly coated on the surface of the NH4Cl template to the maximum extent, avoid the agglomeration of the metal salt and the glucose, and finally ensure the in-situ growth morphology of the metal particles with nanometer sizes on a carbon skeleton obtained by carbonizing the glucose.
After the precursor mixed powder is obtained, the precursor mixed powder is calcined in a reducing atmosphere to obtain the battery negative electrode material.
In the present invention, the reducing atmosphere is preferably a mixed atmosphere of argon and hydrogen; the partial pressure of hydrogen in the mixed atmosphere of argon and hydrogen is preferably 5% to 20%, more preferably 10%.
In the invention, the calcining temperature is preferably 900 ℃, and the heat preservation time is preferably 2-4 h, and more preferably 2.5-3.5 h.
In the calcining process, a carbon source is subjected to carbonization reaction, the graphene obtained by carbonizing glucose is thinner by using a template agent, and meanwhile, a gallium source and an indium source are decomposed into metal GaIn liquid metal particles in a reducing atmosphere and are uniformly loaded on the surface of the graphene.
The invention also provides a battery cathode material prepared by the preparation method in the technical scheme, which comprises graphene and liquid metal particles loaded on the surface of the graphene;
the liquid metal particles are GaIn.
In the invention, the mass ratio of the GaIn to the graphene is preferably (5-15): 100, more preferably (8-12): 100.
in the present invention, the particle size of the GaIn is preferably 5 to 1000nm, and more preferably 20 nm.
The invention also provides the application of the battery cathode material in the technical scheme in a lithium metal battery or a lithium ion battery. In the present invention, the application is more preferably an application in a lithium metal battery.
When the battery negative electrode material is applied to a lithium ion battery, the method for applying the battery negative electrode material is not limited in any way, and the battery negative electrode material can be applied as the negative electrode material of the lithium ion battery by adopting a method well known to a person skilled in the art.
When the battery negative electrode material is applied to a lithium metal battery, the battery negative electrode material is preferably applied as a carrier of lithium metal, the method for applying the battery negative electrode material is not limited in any way, and the battery negative electrode material is applied as a negative electrode material of the lithium metal battery after lithium metal is deposited on the surface of the battery negative electrode material by a method well known to a person skilled in the art.
The following examples are provided to illustrate the negative electrode material of the battery, the preparation method and the application thereof in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
15g of ammonium chloride, 1.5g of glucose and 0.3g of GaCl3、0.08gInCl3Mixing with 70g of deionized water, freezing the mixed solution obtained after mixing at-50 ℃ to a frozen state, placing the frozen state in a freeze dryer, and carrying out freeze drying for 20 hours in a vacuum environment of 5Pa to obtain precursor mixed powder;
calcining the precursor mixed powder in a mixed atmosphere of argon and hydrogen (the partial pressure of the hydrogen is 10%), wherein the calcining temperature is 900 ℃, and the calcining time is 2 hours, so that the battery negative electrode material (marked as NH) is obtained4Cl-GaIn @ G, the mass ratio of GaIn to graphene is 5:100, and the particle size of GaIn is 50 nm).
Example 2
15g of ammonium chloride, 1.5g of glucose and 0.3g of GaCl3、0.08gInCl3Mixing with 70g of deionized water, freezing the mixed solution obtained after mixing at-50 ℃ to a frozen state, placing the frozen state in a freeze dryer, and carrying out freeze drying for 24 hours in a vacuum environment of 5Pa to obtain precursor mixed powder;
calcining the precursor mixed powder in a mixed atmosphere of argon and hydrogen (the partial pressure of the hydrogen is 10%), wherein the calcining temperature is 900 ℃, and the calcining time is 4 hours, so that the battery negative electrode material (marked as NH) is obtained4Cl-GaIn @ G, the mass ratio of GaIn to graphene is 5%, and the particle size of GaIn is 20 nm).
Example 3
15g of ammonium chloride, 1.5g of glucose and 0.3g of GaCl3、0.08gInCl3Mixing with 70g of deionized water, freezing the mixed solution obtained after mixing at-50 ℃ to a frozen state, placing the frozen state in a freeze dryer, and carrying out freeze drying for 20min in a vacuum environment of 5Pa to obtain precursor mixed powder;
calcining the precursor mixed powder in a mixed atmosphere of argon and hydrogen (the partial pressure of the hydrogen is 10%), wherein the calcining temperature is 900 ℃, and the calcining time is 6 hours, so as to obtain the battery negative electrode material (marked as NH)4Cl-GaIn @ G, the mass ratio of GaIn to graphene is 5%, and the particle size of GaIn is 1 mu m).
Comparative example
Mixing 15g of ammonium chloride, 1.5g of glucose and 70g of deionized water, freezing the mixed solution obtained after mixing at-50 ℃ to a frozen state, placing the frozen state in a freeze dryer, and freeze-drying for 20 hours in a vacuum environment of 5Pa to obtain precursor mixed powder;
under argonCalcining the precursor mixed powder under the mixed atmosphere of gas and hydrogen (the partial pressure of the hydrogen is 10%), wherein the calcining temperature is 900 ℃, and the calcining time is 4 hours, so that the battery negative electrode material (marked as NH) is obtained4Cl-G)。
Test example
SEM tests were performed on the battery negative electrode materials prepared in examples 1, 2 and 3, and the test results are shown in fig. 1, 2 and 3, in which fig. 1 is an SEM image of the battery negative electrode material prepared in example 1, fig. 2 is an SEM image of the battery negative electrode material prepared in example 2, and fig. 3 is an SEM image of the battery negative electrode material prepared in example 3; as can be seen from fig. 1 to 3, only when the calcination time is 4 hours, the obtained GaIn nanoparticles are uniformly supported on the graphene layer at the optimal size of 10 nm. The calcination time is too short, so that the GaIn is not completely reduced, the particle morphology is poor, the calcination time is too long, the GaIn particles are agglomerated and grown, and the particle size reaches 1 mu m;
mixing the battery negative electrode material prepared in example 1 and a binder in a mass ratio of 4:1 to obtain a working electrode, taking a Li sheet as a reference electrode and a counter electrode, taking Clgard-2400 as a separator (the material is PP polymer), dissolving 1M lithium bistrifluoromethanesulfonylimide (LiTFSI) in 1, 3-Dioxolane (DOL)/ethylene glycol dimethyl ether (DME) (in a volume ratio of 1:1) to obtain a half-cell, setting the potential of the working electrode to 0V, setting the current to 0.5mA, performing a deposition reaction, and setting the deposition time to 1h, 2h and 4h respectively to obtain lithium metal with different deposited capacities, wherein the micro-morphology of the lithium metal is shown in FIG. 4, wherein the capacities of the lithium metal from left to right in FIG. 4 are 0.5mAh, 1.0mAh and 2.0mAh in sequence. As can be seen from fig. 4, after metallic lithium of different capacities is deposited on the surface of the negative electrode material of the battery shown in example 1, the surface of the electrode material is kept smooth and no lithium dendrite is generated.
Preparing the battery cathode material prepared in the example 2 or the battery cathode material prepared in the comparative example into a half battery according to the method;
the half cell is arranged at 1mAh/cm2&1mA/cm2The test results are shown in FIG. 5, and it can be seen from FIG. 5 that the test results of example 2 are shown in FIG. 5The average coulombic efficiency of the half-cell prepared from the cell cathode material after circulating for 400 circles is 99.3%; the capacity retention rate of the half cell prepared by the negative electrode material is better than that of the half cell prepared by the negative electrode material of the comparative example;
the half cell prepared from the battery cathode material described in example 2 was at 2mAh/cm2&2mA/cm2The battery negative electrode material prepared in example 2 has a capacity retention rate of 98.7% after being cycled for 120 cycles in the high-rate charge and discharge process, and has better rate cycling stability, as can be seen from fig. 6, which is shown in fig. 6.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (8)

1. The preparation method of the negative electrode material of the lithium metal battery is characterized by comprising the following steps of:
mixing a soluble gallium source, a soluble indium source, a carbon source, a template agent and water, and freeze-drying to obtain precursor mixed powder;
calcining the precursor mixed powder in a reducing atmosphere to obtain the lithium metal battery negative electrode material;
the carbon source is one or more of glucose, citric acid and ammonium citrate;
the calcining temperature is 900 ℃, and the heat preservation time is 4 hours;
the lithium metal battery negative electrode material comprises graphene and liquid metal particles loaded on the surface of the graphene;
the liquid metal particles are GaIn.
2. The preparation method according to claim 1, wherein the mass ratio of the template agent, the carbon source, the soluble gallium source and the soluble indium source is (10-20): (1-2): (0.2-0.4): (0.05-0.1);
the mass ratio of the carbon source to the water is 1 (60-100).
3. The method according to claim 1 or 2, wherein the template is one or more of ammonium chloride, sodium chloride and sodium carbonate.
4. The method of claim 1 or 2, wherein the soluble gallium source is GaCl3And/or Ga (NO)3)3；
The soluble indium source is InCl3And/or In (NO)3)3。
5. The method according to claim 1, wherein the freeze-drying is carried out at-50 ℃ under a pressure of 1 to 30Pa for 20 to 48 hours.
6. The negative electrode material for the lithium metal battery prepared by the preparation method of any one of claims 1 to 5, which is characterized by comprising graphene and liquid metal particles loaded on the surface of the graphene;
the liquid metal particles are GaIn.
7. The lithium metal battery negative electrode material as claimed in claim 6, wherein the mass ratio of the GaIn to the graphene is (5-15): 100.
8. use of the lithium metal battery anode material of claim 6 or 7 in a lithium metal battery.
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