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CN110660967B - Lithium battery cathode and preparation method thereof - Google Patents

Lithium battery cathode and preparation method thereof Download PDF

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Publication number
CN110660967B
CN110660967B CN201810697214.7A CN201810697214A CN110660967B CN 110660967 B CN110660967 B CN 110660967B CN 201810697214 A CN201810697214 A CN 201810697214A CN 110660967 B CN110660967 B CN 110660967B
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lithium
metal
alloy
framework
negative electrode
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CN110660967A (en
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王亚龙
陈强
牟翰波
孔德钰
孙青海
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Zhongneng Zhongke Tianjin New Energy Technology 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed materials
    • H—ELECTRICITY
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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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H01M4/742—Meshes or woven material; Expanded metal perforated material
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    • 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

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Abstract

The invention discloses a lithium battery cathode and a preparation method thereof. The lithium battery cathode comprises a metal lithium or lithium alloy composite material, consists of a polymer supporting framework with a porous network structure and a metal lithium or lithium alloy, wherein the polymer supporting framework has lithium ion conduction capability, and the metal lithium or lithium alloy is combined on the supporting framework.

Description

Lithium battery cathode and preparation method thereof
Technical Field
The invention belongs to the technical field of energy batteries, and particularly relates to a lithium battery negative electrode and a manufacturing method thereof.
Background
The lithium metal as the negative electrode of the lithium battery can greatly improve the energy density of the battery, but has not been commercialized, and the main reason is that: (1) The preparation of the metal lithium belt with the thickness accurately controllable is lacking, so that the waste of the metal lithium is avoided, and the utilization rate of the cathode is improved; (2) In the metal lithium circulation process, dendrite is formed on the surface of the lithium cathode to cause potential safety hazard, and on the other hand, the electrolyte/metal lithium interface is continuously evolved to cause the increase of the internal resistance of the battery and the deterioration of the circulation performance.
In the aspect of preparing an ultra-thin lithium strip, the conventional rolling method is used for preparing the metal lithium with the thickness of less than 100 mu m, so that continuous production is difficult, and the ultra-thin metal lithium strip cannot be prepared. The method of coating molten metal lithium on the pole material is difficult to spread uniformly due to the fact that the metal lithium has very large surface tension and poor wettability of the pole material, meanwhile, the whole process needs to be carried out in pure argon or vacuum environment, production continuity is poor, and production efficiency is low.
In the aspect of the metal lithium cathode with high cycle stability, the powder of the metal lithium-framework carbon material can be used as an electrode, so that dendrite formation can be effectively inhibited, and the volume expansion of the electrode can be relieved. The two phases of the metal lithium and the conventional framework carrier are combined to form the flexible electrode, and the surface tension of the liquid metal lithium is large, so that the liquid metal lithium is difficult to combine with the carrier material, and gaseous metal lithium molecules are also poor in adhesion with the carrier, so that the two-phase structure of the electrode in the subsequent process is separated, in addition, the electrode still has the problem of expansion in the deep discharge process, and the long-term circulation of the circulation is not facilitated.
Disclosure of Invention
In order to solve the technical problems, the invention provides a lithium battery negative electrode and a preparation method thereof, wherein the lithium battery negative electrode comprises a metal lithium or lithium alloy composite material with a supporting framework.
The technical scheme adopted by the invention comprises the following steps:
in some embodiments, a lithium battery anode is provided that includes a metal lithium or lithium alloy composite with a support framework that is comprised of a polymeric support framework having a porous network of lithium ion conducting capability and a metal lithium or lithium alloy bonded to the support framework.
The material of the polymeric support scaffold may include: at least one polymer material selected from Polyacrylonitrile (PAN), polymethyl acrylate (PMMA), polyvinylidene fluoride (PVDF), polyethylene glycol (PEG), polyethylene oxide (PEO), or a mixture of at least one of the above polymer materials and a lithium ion conductive inorganic compound.
The lithium ion conductive inorganic compound may include at least one of lithium lanthanum zirconium oxide nanoparticles, lithium sulfur phosphorus compound nanoparticles, aluminum oxide nanoparticles, tin oxide nanoparticles, lithium perchlorate, lithium iodide, lithium nitrate, and lithium bistrifluoromethane sulfonyl imide; and the weight ratio of the lithium ion conductive inorganic compound to the polymeric material in the mixture of the polymeric material and the lithium ion conductive inorganic compound may be 1:5 to 1:100, preferably 1:10 to 1:50.
The polymeric support scaffold may be prepared by an electrospinning or solution coating process.
The polymeric support matrix may have a porosity of 20-99% with a pore size of 1 μm to 200 μm, preferably a porosity of greater than 90%, and a void of greater than 50 μm.
The polymeric support scaffold may have a thickness of 1 μm to 500 μm, preferably 5 μm to 200 μm.
The metallic lithium or lithium alloy may be bonded to the polymeric support framework by vapor deposition. The metallic lithium or lithium alloy may cover the surface of the polymeric support matrix and the pores of the matrix.
The lithium alloy may contain at least one alloy component of Ag, al, au, ba, be, bi, ca, cd, co, cr, cs, fe, ga, ge, hf, hg, in, ir, K, mg, mn, mo, N, na, nb, ni, pt, pu, rb, rh, se, si, sn, sr, ta, te, ti, TI, V, zn, zr, pb, pd, sb, cu in addition to elemental Li; preferably, the lithium alloy contains 50 to 99.99 mass percent of lithium.
The mass ratio of lithium in the metal lithium or lithium alloy composite material with the support framework can be 20-90 weight percent, preferably more than 30 weight percent.
In some embodiments, a method for preparing the negative electrode of the lithium battery is provided, which comprises:
dispersing at least one polymer material selected from Polyacrylonitrile (PAN), polymethyl acrylate (PMMA), polyvinylidene fluoride (PVDF), polyethylene glycol (PEG) and polyethylene oxide (PEO), or a mixture of at least one of the polymer materials and lithium ion conductive inorganic compound in an organic solvent, then carrying out electrostatic spinning or solution coating on the obtained dispersion or solution to prepare a polymer support framework with a porous network structure capable of lithium ion conductivity,
depositing metal lithium or lithium alloy on the polymer support framework by a vapor deposition method to obtain a metal lithium or lithium alloy composite material with the support framework;
the obtained metal lithium or lithium alloy composite material with the support framework is directly used as a lithium battery cathode.
The organic solvent may include N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), para-xylene (PX), tetrahydrofuran (THF), ethanol, acetonitrile (AN), etc.
The metallic lithium or lithium alloy may be deposited onto the polymeric support matrix by vapor deposition. Vapor deposition methods may include vacuum evaporation. For example, at 10 -1 Pa-10 -6 Pa (preferably 10 -2 -10 -5 Pa), the metallic lithium or lithium alloy target is heated to a temperature capable of evaporating lithium or lithium alloy, for example, a temperature of 500 to 1500 c (preferably 600 to 1300 c), and evaporated onto the polymer support skeleton.
In the vapor deposition method, the polymer support matrix may be attached to a chill roll and rotated at a speed of, for example, 10rpm to 200 rpm. The deposition time may be 5-100 minutes.
The invention has at least one of the following beneficial effects:
(1) The metal lithium or lithium alloy composite material with the support framework has a lithium ion and electron conducting network, can provide good lithium ion and electron path frameworks, and ensures the stability of an electrode structure in the deep discharge process. The mechanism may be as follows: the framework material has lithium ion conduction capability, combines the conductive characteristic of the metal lithium, and the lithium ions are conducted along the framework, so that electrons are obtained at the place where the metal lithium exists, and the metal lithium is deposited. The mechanism can determine that the lithium ion deposition is uniform, and provides sites and spaces for the lithium ion deposition through a porous structure, so that the structural stability of the electrode can be ensured. Moreover, the principle of keeping the electrode structure stable is that metallic lithium and a framework material are cooperatively formed together.
(2) The metal lithium or lithium alloy composite material with the supporting framework still maintains the characteristics of low potential and high capacity of the metal lithium, and effectively inhibits dendrite formation in circulation.
(3) The metallic lithium or lithium alloy composite material with a supporting framework of the present invention can be directly used as a negative electrode of a lithium ion battery, for example, a negative electrode of a lithium secondary battery.
(4) The metal lithium or lithium alloy composite material with the support framework can be used for a lithium battery with liquid electrolyte and is also suitable for an all-solid-state lithium battery.
(5) The support framework is a flexible polymer substrate, so that the electrode has good flexibility, can be bent at will, can realize roll-to-roll production, accurately controls the thickness and the width of the electrode, and improves the production efficiency.
(6) The support structure is a compound, provides good mechanical support, ensures the ultra-thin thickness condition, can prepare the ultra-wide electrode, and has good operability.
(7) The support matrix of the present invention may be doped with particles of lithium ion conductive inorganic compounds in the conductive polymer material. These inorganics have very high lithium ion conductivity per se, but are inflexible, and doping these inorganics in a polymeric material can increase the conductivity of lithium ions and overcome the disadvantage of inflexibility per se.
(8) According to the invention, the lithium alloy can be loaded on the supporting framework, so that on one hand, the surface tension of metal lithium can be reduced, the wettability and the adhesion are improved, and on the other hand, a good lithium ion and electron path framework can be provided, and the stability of the electrode structure in the deep discharge process is ensured.
Drawings
Fig. 1 is a constant current charging curve of the lithium composite with support framework prepared in example 1.
FIG. 2 is a scanning electron microscope image of the skeletal support prepared in example 2.
FIG. 3 is a scanning electron microscope image of the metal lithium composite with supporting framework prepared in example 3.
Fig. 4 is a graph showing the cycle performance of the battery of example 5.
Fig. 5 is a schematic view of the cycle performance of the battery of example 6.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Also, the various product structural parameters, various reaction participants and process conditions employed in the following examples are typical examples, but a great deal of experiments by the inventor prove that the above-listed other different structural parameters, other types of reaction participants and other process conditions are applicable and can achieve the technical effects claimed in the invention.
Example 1
Lithium lanthanum zirconium oxide nano-powder (Li) 7 La 3 Zr 2 O 12 Particle size 500 nm), polymethyl methacrylate (PMMA molecular weight 10 ten thousand), according to mass ratio 1:10 are dispersed in N, N-Dimethylformamide (DMF) solution, uniformly mixed, and the skeleton carrier is prepared by an electrostatic spinning method with the direct current voltage of 10 KV. Then the skeleton carrier is put into a thermal evaporation chamber, a metal lithium target is added at the same time, the vacuum is pumped, and the pressure of the chamber body reaches 10 -2 Pa, turning on a heating source, adjusting the temperature to 600 ℃, turning on circulating cooling water at the same time, evaporating, continuously performing evaporation for 30min, ending evaporation, and cooling to room temperature to obtain the metal lithium compound with the supporting framework.
The thickness of the prepared skeleton carrier is 50 micrometers, and the porosity of the skeleton carrier is tested by adopting a bubble pressure method
50%, after which the specific capacity of the compound was measured by constant current charging to 1560mAh/g (see FIG. 1), the content of reduced lithium was 40wt%.
The bubble pressure method comprises the following testing steps: soaking the carrier in ethanol solution, removing excessive ethanol on the surface of the carrier by using filter paper, placing the carrier in a 3H-2000PB type bubble pressure method filter membrane pore size analyzer, applying air pressure on one side of the membrane, and discharging the ethanol absorbed in the pores of the carrier until all the pores are opened.
The "reduced lithium content" is a value obtained by measuring the specific capacity of the metallic lithium or lithium alloy composite material, compared with the highest specific capacity of metallic lithium (3860 mAh/g).
Example 2
Lithium bistrifluoromethane sulfonyl imide inorganic powder (LiTFSI), lithium nitrate (LiNO) 3 ) Polyvinylidene fluoride (PVDF, molecular weight 15 ten thousand) according to a mass ratio of 1:1:20 are dispersed in N-methyl pyrrolidone (NMP) solution, uniformly mixed, and the skeleton carrier is prepared by an electrostatic spinning method with a direct current voltage of 10 KV. Then the skeleton carrier is put into a thermal evaporation chamber, a metal lithium target is added at the same time, the vacuum is pumped, and the pressure of the chamber body reaches 10 -2 Pa, turning on a heating source, adjusting the temperature to 700 ℃, turning on circulating cooling water at the same time, evaporating, continuously performing evaporation for 60min, ending evaporation, and cooling to room temperature to obtain the-metal lithium composite with the supporting framework, wherein a scanning electron microscope image is shown in figure 2.
The thickness of the prepared skeleton carrier is 20 micrometers, the porosity of the original skeleton carrier is 80% by a bubble pressure method, and then the specific capacity of the compound is 3000mAh/g by constant current charging test, so that the content of the compound is 78wt%.
Example 3
Lithium sulfur phosphorus inorganic powder (Li) 2 S-P 2 S 5 Particle size of 200 nm), polyethylene glycol (PEG, molecular weight of 10
Ten thousand), according to the mass ratio of 1:20 are dispersed in para-xylene (PX) solution, mixed uniformly, coated on glass by a doctor blade, and then dried at 120 ℃. Then the skeleton carrier is put into a thermal evaporation chamber, a metal lithium target is added at the same time, the vacuum is pumped, and the pressure of the chamber body reaches 10 -2 Pa, turning on a heating source, regulating the temperature to 800 ℃, simultaneously turning on circulating cooling water, evaporating, continuously performing evaporation for 60min, ending evaporation, and cooling to room temperatureA metal lithium complex with a supporting framework is obtained, and a scanning electron microscope diagram of the metal lithium complex is shown in fig. 3.
The thickness of the prepared skeleton carrier is 150 micrometers, the porosity of the original skeleton carrier is 70 percent by adopting a bubble pressure method, the specific capacity of the compound is 2100mAh/g by constant current charging, and the content of folded lithium is 54
wt％。
Example 4
Using the skeletal support prepared in example 1, placing the skeletal support in a thermal evaporation chamber, using a lithium aluminum alloy (wherein the mass fraction of aluminum is 0.5%) target, evacuating, and keeping the chamber pressure at 10 -2 Pa, turning on a heating source, adjusting the temperature to 750 ℃, turning on circulating cooling water at the same time, evaporating, continuously performing evaporation for 40min, ending evaporation, and cooling to room temperature to obtain the lithium alloy negative electrode belt with the supporting framework.
Example 5
Preparation of a Battery, lithium iron phosphate positive plate with a diameter of 15 mm (Shenzhen Kogyo Co., ltd., aluminum foil thickness of 15 μm, single-sided active material surface density of 2.7 mAh/cm) 2 ) As the positive electrode of the simulated battery, the electrolyte was 1mol/LLiPF 6 EC/DMC/EMC (vol 1/1/1), the membrane was a PP membrane. The battery test conditions were 250 cycles at 0.5C with a voltage range of 4.1V-2.5V. The negative electrode is the lithium composite material with supporting framework (curve 1) prepared in example 3, and in addition, a metal lithium sheet (curve 2) is adopted as a comparative experiment, fig. 4 shows the cycle performance of the battery composed of different negative electrodes, after 250 cycles, the capacity of the battery using the composite material with supporting framework as the negative electrode is not obviously attenuated, and after 50 cycles, the battery using the metal lithium sheet as the negative electrode can not work any more.
Example 6
Preparation of a Battery, a lithium Nickel cobalt manganese oxide positive plate with a diameter of 15 mm (Nanew energy technology Co., ltd., suzhou, aluminum foil thickness 15 μm, single-sided active material surface density 3 mAh/cm) 2 ) As the positive electrode of the simulated battery, the electrolyte was 1mol/L LiPF 6 EC/DMC/EMC (vol 1/1/1), 10wt% FEC as additive, separator was PP separator. The battery test conditions were 0.5C 250 cycles, electricityThe pressure range is 4.1V-2.5V. The formation was performed at 0.1C, followed by cycling at 0.5C magnification. The negative electrode is the lithium composite material with supporting framework (curve 1) prepared in example 4, and a metal lithium sheet (curve 2) is additionally adopted as a comparison experiment, and fig. 5 shows the cycle performance of the batteries with different negative electrode compositions. As can be seen from the figure, the battery with the metal lithium negative electrode composition with the support skeleton exhibited better cycle performance.
It should be understood that the foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the invention, but is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (7)

1. A lithium battery negative electrode comprising a metal lithium or lithium alloy composite material with a support framework, the metal lithium or lithium alloy composite material consisting of a polymer support framework having a porous network structure with lithium ion conductivity and a metal lithium or lithium alloy bonded to the support framework, wherein
The polymer supporting framework is obtained by electrostatic spinning of a mixture of lithium ion conductive inorganic compound and at least one polymer material selected from polyethylene oxide, polyacrylonitrile, polymethyl acrylate, polyvinylidene fluoride and polyethylene glycol,
the lithium ion conductive inorganic compound comprises at least one of lithium lanthanum zirconium oxide nano-particles, lithium sulfur phosphorus compound nano-particles, lithium perchlorate, lithium iodide, lithium nitrate and lithium bistrifluoromethane sulfonyl imide,
the polymer support skeleton has 20-99% porosity, pore size of 1-200 μm,
the metallic lithium or lithium alloy is bonded to the polymeric support matrix by vapor deposition,
the mass ratio of lithium in the metal lithium or lithium alloy composite material with the supporting framework is 20-90.
2. The lithium battery negative electrode of claim 1, wherein the weight ratio of the lithium ion conductive inorganic compound to the polymeric material is from 1:5 to 1:100.
3. The lithium battery anode of claim 1, wherein the polymeric support matrix has a thickness of 1 μιη to 500 μιη.
4. The lithium battery negative electrode according to claim 1, wherein the lithium alloy contains at least one alloy component of Ag, al, au, ba, be, bi, ca, cd, co, cr, cs, fe, ga, ge, hf, hg, in, ir, K, mg, mn, mo, N, na, nb, ni, pt, pu, rb, rh, se, si, sn, sr, ta, te, ti, V, zn, zr, pb, pd, sb, cu in addition to elemental Li.
5. The negative electrode of lithium battery according to claim 1, wherein the lithium alloy contains 50 to 99.99 mass% of lithium.
6. A method of making a negative electrode for a lithium battery of any one of claims 1-5, the method comprising:
dispersing at least one polymer material selected from polyacrylonitrile, polymethyl acrylate, polyvinylidene fluoride, polyethylene glycol and polyethylene oxide and a mixture of lithium ion conductive inorganic compounds in an organic solvent, then carrying out electrostatic spinning on the obtained dispersion liquid to prepare a polymer support framework with a porous network structure and lithium ion conductive capability,
depositing metal lithium or lithium alloy on the polymer support framework by a vapor deposition method to obtain a metal lithium or lithium alloy composite material with the support framework;
the obtained metal lithium or lithium alloy composite material with the support framework is directly used as a lithium battery cathode.
7. The method of claim 6, wherein the organic solvent comprises at least one of N, N-dimethylformamide, N-methylpyrrolidone, para-xylene, tetrahydrofuran, ethanol, acetonitrile.
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