CN117352705B - Superlattice synergistic glass-based battery positive electrode material and preparation method thereof - Google Patents

Superlattice synergistic glass-based battery positive electrode material and preparation method thereof Download PDF

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CN117352705B
CN117352705B CN202311638498.XA CN202311638498A CN117352705B CN 117352705 B CN117352705 B CN 117352705B CN 202311638498 A CN202311638498 A CN 202311638498A CN 117352705 B CN117352705 B CN 117352705B
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CN117352705A (en
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杜晓莹
王舒成
王朝阳
张宪玺
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Shandong Xinxian Huayang Industrial Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
    • 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
    • H01M4/362—Composites
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a superlattice synergistic glass-based battery positive electrode material and a preparation method thereof. The molar percentage composition of the positive electrode material is xLi 2 O‑(100‑2x)V 2 O 5 ‑xP 2 O 5 The value of x is 5-45%. The preparation method of the positive electrode material comprises the following steps: (1) Preparing raw material Li according to the molar composition of the positive electrode material 2 O、V 2 O 5 And P 2 O 5 . And then mixing the raw materials, performing melting treatment, and quenching the obtained melt to obtain the glass body. (2) And carrying out heat treatment on the glass body under the air atmosphere and the temperature condition of 280-300 ℃, and cooling to room temperature after finishing the heat treatment to obtain the positive electrode material. The positive electrode material can be prepared without being under protective atmosphere, and the electronic/ionic conductivity of the positive electrode material is greatly improved by utilizing a superlattice structure, so that the reversible capacity and the rate capability are remarkably improved.

Description

Superlattice synergistic glass-based battery positive electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of battery anode materials, in particular to a superlattice synergistic glass-based battery anode material and a preparation method thereof.
Background
The positive electrode material is the most critical component determining the overall electrochemical performance of the lithium ion battery. At present, one of the sources of the problem that the commercial lithium ion battery suffers from unsatisfactory energy density is that the theoretical specific capacity of the cathode material is low. V (V) 2 O 5 Is a lithium ion battery anode material with application potential, and the theoretical specific capacity of the lithium ion battery anode material is up to 440 mAh.g -1 Is 2.5 times of the theoretical specific capacity of the current commercial lithium iron phosphate anode material. However, crystalline V 2 O 5 As a positive electrode material, irreversible crystal form transformation occurs during charge and discharge, thereby causing serious capacity decay. Glass is a material free of crystalline phases, and therefore vitrification becomes a solution to V 2 O 5 Optimal strategy for irreversible phase change reaction of the positive electrode material.
The preparation of vanadium-based glass positive electrode materials for lithium ion batteries has attracted attention from scientists. For example, patent document CN 114044631A selects series of lithium-containing and vanadium-containing materials, and prepares a material with high electron conductivity (3×10 under strong reducing agent and inert atmosphere -5 ~5×10 -4 S/cm) of lithium-containing vanadate glass. The glass is used as a lithium ion battery anode material and shows 296-342 mAh.g -1 And a coulombic efficiency of 95.8 to 98%. Patent document publication No. CN 111668468A prepares a vanadium pentoxide-lithium borate-graphene glass positive electrode material for a lithium ion battery under a protective atmosphere. Electrochemical tests show that the initial discharge capacity of the positive electrode material is 403-424 mAh.g -1 The residual discharge capacity after one hundred circles of circulation is 389-394 mAh.g -1 。
Although the vanadium-based glass lithium battery positive electrode material prepared by the above technology has good performance in terms of discharge capacity and cycle performance, the conditions under which preparation is required in a protective atmosphere bring additional difficulties and challenges to industrial production.
Disclosure of Invention
In view of the above, the invention discloses a superlattice synergistic glass-based battery positive electrode material and a preparation method thereof, wherein the positive electrode material can be prepared without a protective atmosphere, and the electronic/ionic conductivity of the positive electrode material is greatly improved by utilizing a superlattice structure, so that the reversible capacity is remarkably improved. In order to achieve the above object, the present invention discloses the following technical solutions.
First, the invention discloses a superlattice synergistic glass-based battery positive electrode material, the molar percentage composition of which is xLi 2 O-(100-2x)V 2 O 5 -xP 2 O 5 Wherein: the value range of x is 5-45%.
Secondly, the invention discloses a preparation method of the superlattice synergistic glass-based battery anode material, which comprises the following steps:
(1) Preparing raw material Li according to the molar composition of the positive electrode material 2 O、V 2 O 5 And P 2 O 5 . And then mixing the raw materials, performing melting treatment at 900 ℃, and quenching the obtained melt to obtain the glass body.
(2) And carrying out heat treatment on the glass body in an air atmosphere, and cooling to room temperature after finishing the heat treatment to obtain the positive electrode material.
Further, in the step (1), the raw materials are mixed and then ground so as to fully mix the raw materials.
In step (1), the method of quenching is to pour the melt into water.
Further, in the step (2), the heat treatment temperature is 280-300 ℃, and the heat preservation time is 0-4 hours.
Compared with the prior art, the invention has the following beneficial technical effects: the process of the invention is characterized in that the temperature and the duration of the heat treatment are precisely controlled in Li 2 O-V 2 O 5 -P 2 O 5 Superlattice structures are grown in the glass matrix. This unique structure would bring two benefits to the glass-based positive electrode materials described above. 1. Improving the electronic conductivity: electrons in the superlattice structure can generate resonance tunneling effect under the action of the applied voltage, and the electron transmission potential barrier is reduced, so that the electron transmission potential barrier is improvedElectron conductivity of the composite positive electrode material. 2. Improving ionic conductivity: the superlattice is an artificial super structure with a larger repetition period of structural units, wherein layered crystal materials are arranged according to a certain rule. The greater structural periodicity provides additional and broad transport channels for lithium ion transport, and therefore, the ionic conductivity in the composite positive electrode material is improved. Under the effect of jointly improving the ionic conductivity and the electronic conductivity, the reversible capacity and the multiplying power performance of the composite anode material are obviously improved. In addition, the composite positive electrode material designed by the invention also has the technical advantages of no need of protective atmosphere in the production process and no irreversible phase change in the charge and discharge process, and is an effective scheme which has industrial production conditions and can solve the urgent requirement of high reversible capacity of the positive electrode material.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. Embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is an XRD pattern for LVP-90, LVP-70, LVP-50, LVP-30 and LVP-10 samples prepared in the following examples.
FIG. 2 shows the electrochemical performance comparisons of LVP-90, LVP-70, LVP-50, LVP-30 and LVP-10 samples prepared in the following examples.
FIG. 3 is a differential scanning calorimetric profile (DSC) of a LVP-70 sample prepared in the following example.
FIG. 4 is an X-ray diffraction (XRD) pattern of LVP-70, LVP-70-1, LVP-70-2, LVP-70-3, LVP-70-4 and LVP-70-5 samples prepared in the following examples.
FIG. 5 is a High Resolution Transmission Electron Microscope (HRTEM) image of LVP-70-1 samples prepared in the following examples.
FIG. 6 is a HRTEM image of LVP-70-2 samples prepared in the examples.
FIG. 7 is a HRTEM image of LVP-70-3 samples prepared in the examples.
FIG. 8 is a HRTEM image of LVP-70-4 samples prepared in the examples.
FIG. 9 is a HRTEM image of LVP-70-5 samples prepared in the examples.
FIG. 10 is an electrochemical impedance profile of LVP-70, LVP-70-1, LVP-70-2, LVP-70-3, LVP-70-4 and LVP-70-5 samples prepared in the following examples.
FIG. 11 shows the samples of LVP-70, LVP-70-1, LVP-70-2, LVP-70-3, LVP-70-4 and LVP-70-5 prepared in the following examples at 50 mAh.g -1 Is a graph of reversible specific capacity under current density conditions.
FIG. 12 shows LVP-70, LVP-70-1, LVP-70-2, LVP-70-3, LVP-70-4 and LVP-70-5 samples prepared in the following examples at 1600 mAh.g -1 Is a graph comparing cycle-to-cycle performance under current density conditions.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or materials used in the present invention may be purchased in conventional manners, and unless otherwise indicated, they may be used in conventional manners in the art or according to the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The invention will now be further described with reference to the drawings and detailed description, wherein preferred embodiments and materials are described, by way of illustration only.
Example 1
Superlattice synergistic glass-based battery positive electrode material xLi 2 O-(100-2x)V 2 O 5 -xP 2 O 5 The preparation method of (2) comprises the following steps:
(1) Raw material Li of the positive electrode material was prepared at x=5%, 15%, 25%, 35%, and 45% 2 O、V 2 O 5 And P 2 O 5 . These materials are mixedAnd (5) fully grinding in a ball mill to obtain precursor mixed powder.
(2) And pouring the precursor mixed powder into a corundum crucible, then placing the corundum crucible into a muffle furnace, melting the precursor mixed powder at 900 ℃ in an air atmosphere, and preserving the heat for 2 hours.
(3) And (3) pouring the melt obtained in the step (2) into deionized water at normal temperature for quenching to obtain a glass material, and sequentially named as LVP-90, LVP-70, LVP-50, LVP-30 and LVP-10.
XRD patterns of the LVP-90, LVP-70, LVP-50, LVP-30 and LVP-10 samples are shown in FIG. 1, all of which had one broad peak representing amorphous at 20℃and only LVP-90 samples observed weak diffraction peaks. Indicating that all samples were amorphous matrix and that only small amounts of crystals were present in the LVP-90 samples. The results of the electrochemical test show (FIG. 2), LVP-70 at 50 mAh.g -1 The reversible discharge capacity at the current density of (3) was about 240 mAh g -1 At 1600 mAh.g -1 The initial specific discharge capacity at the current density of (3) was about 60 mAh g -1 . These two data are significantly better for the LVP-70 samples than for the other samples, and therefore, the LVP-70 component samples were used as the basis for subsequent processing.
Example 2
Superlattice synergistic glass-based battery positive electrode material xLi 2 O-(100-2x)V 2 O 5 -xP 2 O 5 The preparation method of (2) comprises the following steps:
(1) LVP-70 glass Material was prepared as described in example 1
(2) After the resultant glass material was pulverized and sufficiently ground, a DSC curve (as shown in fig. 3) was tested, and the glass material was incubated at a temperature of 2 h at which the starting temperature of the first crystallization peak of the DSC curve, i.e., 287 ℃, and the resultant glass-based battery positive electrode material was designated as LVP-70-1.
From the XRD pattern (FIG. 4), no distinct crystal diffraction peaks were found in the LVP-70-1 sample, and from the HRTEM pattern (FIG. 5), many superlattice structures of uniform size and perfect morphology were clearly observed. In combination with the above test results, it was confirmed that crystals were precipitated in the LVP-70-1 sample and that these crystals also grew into a superlattice structure, but the content of crystals and superlattice was also relatively small.
LVP-70-1 sample prepared in this example was used as positive electrode material, metallic lithium sheet as corresponding electrode, commercial PP film as separator to assemble LVP-70-1 Li half cell and its electrochemical performance was tested. The charge transfer impedance of the cell is 82 Ω (as shown in fig. 10); at 50 mAh.g -1 The reversible discharge capacity at the current density of (2) is about 290 mAh.g -1 As shown in FIG. 11, at 1600 mAh.g -1 The initial discharge specific capacity at the current density of (3) was about 180 mAh g -1 The remaining capacity after 200 cycles is about 85 mAh.g -1 (as shown in fig. 12).
Example 3
Superlattice synergistic glass-based battery positive electrode material xLi 2 O-(100-2x)V 2 O 5 -xP 2 O 5 The preparation method of (2) comprises the following steps:
(1) LVP-70 glass materials were prepared as described in example 1.
(2) The resultant glass material was pulverized and sufficiently ground, then placed in a muffle furnace, and heat-treated at 287 ℃ for 1 h, and the resultant glass-based battery positive electrode material was designated as LVP-70-2.
From the XRD pattern (FIG. 4), no distinct crystal diffraction peaks were found in the LVP-70-2 sample, and from the HRTEM pattern (FIG. 6), a small number of crystalline regions and superlattice regions were clearly observed. In addition, the crystalline and superlattice regions occupy a smaller area. These phenomena indicate that crystals are precipitated in the LVP-70-2 sample and that these crystals also grow to a superlattice structure, but the content of crystals and superlattice is less than in the LVP-70-1 sample.
The LVP-70-2 sample prepared in this example was used as a positive electrode material, a metallic lithium sheet was used as a corresponding electrode, a commercial PP film was used as a separator, and an LVP-70-2 Li half cell was assembled and tested for electrochemical performance. The charge transfer impedance of the cell was 321 Ω (as shown in fig. 10); at 50 mAh.g -1 Reversible discharge capacity at current density of (3)About 223 mAh.g -1 As shown in FIG. 11, at 1600 mAh.g -1 The initial specific discharge capacity at the current density of (3) was about 96 mAh g -1 The remaining capacity after 200 cycles was about 57 mAh g -1 (as shown in fig. 12).
Example 4
Superlattice synergistic glass-based battery positive electrode material xLi 2 O-(100-2x)V 2 O 5 -xP 2 O 5 The preparation method of (2) comprises the following steps:
(1) LVP-70 glass materials were prepared as described in example 1.
(2) The glass material was crushed and sufficiently ground, then placed in a muffle furnace, and incubated at 287 ℃ for 4 h, and the resulting glass-based battery positive electrode material was designated as LVP-70-3.
The XRD pattern of the LVP-70-3 sample is shown in FIG. 4, and it can be seen that a crystal diffraction peak was found at 26℃in the pattern. HRTEM of LVP-70-3 samples as shown in fig. 7, a large area of superlattice structure was clearly observed from fig. 7, and these superlattice structures were stacked, indicating that prolonged heat treatment, while promoting crystal and superlattice growth, overgrowth could disrupt the superlattice structure integrity.
LVP-70-3 glass prepared in the embodiment is used as a positive electrode material, a metal lithium sheet is used as a corresponding electrode, a commercial PP film is used as a diaphragm to assemble an LVP-70-3 Li half cell, and electrochemical performance of the LVP-70-3 Li half cell is tested. The charge transfer impedance of the cell is 179 Ω (as shown in fig. 10); at 50 mAh.g -1 The reversible discharge capacity at the current density of (2) was about 252 mAh g -1 As shown in FIG. 11, at 1600 mAh.g -1 The initial discharge specific capacity at the current density of (3) was about 103 mAh g -1 The remaining capacity after 200 cycles was about 70 mAh g -1 (as shown in fig. 12).
Example 5
Superlattice synergistic glass-based battery positive electrode material xLi 2 O-(100-2x)V 2 O 5 -xP 2 O 5 The preparation method of (2) comprises the following steps:
(1) LVP-70 glass materials were prepared as described in example 1.
(2) The obtained glass material is crushed and fully ground, then is placed in a muffle furnace, and is insulated at 280 ℃ for 4 h, thus obtaining the glass-based battery anode material which is named as LVP-70-4.
The XRD pattern of the LVP-70-4 sample is shown in FIG. 4, from which no distinct crystal diffraction peak was observed. From the HRTEM pictures (fig. 8) a very small number of crystalline regions and incomplete superlattice regions can clearly be observed. These phenomena indicate that the LVP-70-4 sample is in the initial stage of crystallization, but the crystal content is far lower than that of the LVP-70-1 sample, and the superlattice structure is not grown completely.
The LVP-70-4 sample prepared in the example is used as a positive electrode material, a metal lithium sheet is used as a corresponding electrode, a commercial PP film is used as a diaphragm to assemble an LVP-70-4 Li half cell, and the electrochemical performance of the LVP-70-4 Li half cell is tested. The charge transfer impedance of the cell is about 350 Ω (as shown in fig. 10); at 50 mAh.g -1 The reversible discharge capacity at the current density of (3) was about 216 mAh g -1 As shown in FIG. 11, at 1600 mAh.g -1 The initial specific discharge capacity at the current density of (3) was about 78 mAh g -1 The remaining capacity after 200 cycles was about 65 mAh g -1 (as shown in fig. 12).
Example 6
Superlattice synergistic glass-based battery positive electrode material xLi 2 O-(100-2x)V 2 O 5 -xP 2 O 5 The preparation method of (2) comprises the following steps:
(1) LVP-70 glass materials were prepared as described in example 1.
(2) The obtained glass material is crushed and fully ground, then is placed in a muffle furnace, and is insulated at 300 ℃ for 1 h, and the obtained glass-based battery anode material is named as LVP-70-5.
The XRD pattern of the LVP-70-5 sample is shown in FIG. 4, from which no distinct crystal diffraction peak was observed. From the HRTEM images (fig. 9), a large number of crystalline regions and large-area superlattice regions are clearly observed, and the crystalline regions and superlattice regions overlap, resulting in an incomplete superlattice structure.
LVP-70-5 sample prepared in this example was used as positive electrode material, metallic lithium sheet as corresponding electrode, commercial PP film as separator to assemble LVP-70-5 Li half cell and its electrochemical performance was tested. The charge transfer impedance of the cell is about 196 Ω (as shown in fig. 10); at 50 mAh.g -1 The reversible discharge capacity at the current density of (3) was about 241 mAh g -1 As shown in FIG. 11, at 1600 mAh.g -1 The initial specific discharge capacity at the current density of (3) was about 86 mAh g -1 The remaining capacity after 200 cycles was about 71 mAh g -1 (as shown in fig. 12).
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (3)

1. A superlattice synergistic glass-based battery positive electrode material is characterized in that the molar composition of the positive electrode material is xLi 2 O-(100-2x)V 2 O 5 -xP 2 O 5 Wherein: the value range of x is 5-45; the superlattice synergistic glass-based battery anode material is prepared by the following method:
(1) Preparing raw material Li according to the molar composition 2 O、V 2 O 5 And P 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the Then mixing the raw materials, performing melting treatment, and quenching the obtained melt to obtain a glass body;
(2) Carrying out heat treatment on the glass body in an air atmosphere, and cooling to room temperature after finishing the heat treatment to obtain the anode material;
in the step (2), the heat treatment temperature is 280-300 ℃, and the heat treatment time is 1-4 hours.
2. The superlattice enhanced glass-based battery cathode material according to claim 1, wherein in step (1), the melting temperature is 900 ℃.
3. The superlattice enhanced glass-based battery cathode material according to claim 1, wherein in the step (1), the quenching method is to pour the melt into water.
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