CN112751009A - Zinc aluminate porous carbon based negative electrode material for lithium ion battery and preparation method and application thereof - Google Patents

Zinc aluminate porous carbon based negative electrode material for lithium ion battery and preparation method and application thereof Download PDF

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CN112751009A
CN112751009A CN202110178630.8A CN202110178630A CN112751009A CN 112751009 A CN112751009 A CN 112751009A CN 202110178630 A CN202110178630 A CN 202110178630A CN 112751009 A CN112751009 A CN 112751009A
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lithium ion
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negative electrode
electrode material
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CN112751009B (en
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肖高
李晓慧
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Fuzhou University
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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
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 discloses a zinc aluminate solid solution porous carbon-based negative electrode material for a lithium ion battery and a preparation method thereof, wherein an active substance of the negative electrode material is ZnAl2O4and/C. The problems of low coulombic efficiency, poor cycling stability, low specific capacity, potential safety hazard to a certain degree and the like of the lithium ion battery are solved. Can form the ZnAl2O4the/C composite material is directly used as the cathode of the lithium ion battery. The lithium ion battery provided by the invention has high safety, high coulombic efficiency and good cycle stabilityAnd excellent rate capability, so that ZnAl2O4the/C has great potential application value as the negative electrode material of the lithium ion battery.

Description

Zinc aluminate porous carbon based negative electrode material for lithium ion battery and preparation method and application thereof
Technical Field
The invention belongs to the field of rechargeable battery materials, and particularly relates to a zinc aluminate solid solution porous carbon-based negative electrode material for a lithium ion battery, and a preparation method and application thereof.
Background
Currently, energy shortage and environmental pollution are two major challenges threatening human survival. Fossil fuels have been the major source of energy for human demand, but due to the emission of nitrous oxide, methane, carbon dioxide and other volatile organic compound-containing gases, these resources are rapidly depleting and often causing environmental problems such as air pollution and global warming. Therefore, renewable and clean energy sources must be developed to replace fossil fuels, and wind, solar and tidal energy are good choices of clean energy sources. However, they are generally limited by natural conditions and intermittent uncertainties. Thus, electrochemical energy storage devices can be used to effectively address this problem.
Metal oxides are the most studied energy storage device electrodes at present, e.g. SnO2，Fe3O4，MnO2ZnO and the like have attracted attention because of their high theoretical capacity. Wherein, ZnO has high theoretical specific capacity of 978 mAh/g, which is 1.6 times of that of the traditional graphite (372 mAh/g), and has low cost and environmental friendliness, thereby arousing wide research interest. However, during the cycling process, severe polarization due to the low conductivity of ZnO and irreversible structural degradation due to large volume changes cause a significant capacity loss of the ZnO electrode. To overcome these defects, the preparation of nano-sized ZnO particles is generally used to shorten the diffusion distance of ions, and to combine with conductive materials (carbon nanotubes or graphene), buffer the volume expansion and improve the cycle stability. However, the ZnO electrode still has limitations in practical applications. In recent years, there are a large number of reports in the literature on Al2O3Applied as a coating in a lithium ion battery, not only can be used as a preformed SEI film to reduce the regeneration of the SEI film and the consumption of lithium ions in subsequent cycles, but also Al2O3Has excellent elastic rigidity and mechanical strength, and can reduce volume change of active material during circulation and prevent aggregation of electrochemically active nanoparticles, thereby maintaining electricityStructural integrity of the nano-material, while Al2O3And side reactions between the electrode and the electrolyte can be reduced, and the structure of the cathode material is stabilized.
At present, aluminum salt is introduced to form a bimetal mixed oxide, and the bimetal mixed oxide is applied to a lithium ion battery cathode and is rarely reported. Therefore, the method for preparing ZnAl by adopting the normal-temperature synthesis method which is simple to operate and environment-friendly2O4a/C composite material and is firstly applied to the negative electrode of the lithium ion battery, ZnAl2O4In the first charge-discharge process of the solid solution, the oxidation-reduction reaction is carried out to generate ZnO and Al2O3The lithium ion battery has the advantages of providing high specific capacity and strong mechanical strength for subsequent charge-discharge cycles and improving the electrochemical performance of the lithium ion battery.
Disclosure of Invention
The invention aims to solve the problems of the existing lithium ion battery cathode material and solve the problems of low coulombic efficiency, fast capacity attenuation, low specific capacity, low safety and the like of the common potassium ion battery. Therefore, a porous ZnAl suitable for lithium ion batteries has been developed2O4the/C cathode material has the advantages of high safety, slow capacity decay, excellent rate capability, high coulombic efficiency and the like.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the negative electrode material ZnAl2O4The specific preparation method of the/C comprises the following steps:
(1) 2.97 g of zinc nitrate hexahydrate and 2.46 g of 2-methylimidazole were poured into 50 mL of a methanol solution, and sufficiently dissolved by sonication. Thereafter, the methanol solution containing 2-methylimidazole was slowly poured into the methanol solution containing zinc nitrate hexahydrate. The resulting mixed solution was stirred at 600 rpm for 24 hours at room temperature. Finally, ZIF-8 white powder was obtained by centrifugation, washed with methanol several times, centrifuged, and dried in an oven at 60 ℃.
(2) 0.28 g of aluminum trichloride hexahydrate was sufficiently dissolved in 20 mL of ultrapure water, and mixed with 20 mL of tannic acid solution (10 mg/mL) at room temperatureAfter stirring for 2 h, 0.28 g of ZIF-8 white powder was added and after stirring for another 1 h, a flocculent precipitate appeared in the solution. Then, the precipitate was washed with ultrapure water several times and centrifuged, and the obtained sample was dried in an oven at 60 ℃ and recorded as Al3+/Zn2+-a TA precursor.
(3) Taking a proper amount of the precursor in a square boat, directly heating to 600 ℃ at a constant heating rate (5 ℃/min) in a pure nitrogen atmosphere, and keeping the temperature for 4 h. After the temperature reduction is finished, the ZnAl for the lithium ion battery can be obtained2O4a/C negative electrode material; wherein ZnAl is2O4the/C has a porous structure, and the pore diameter is mainly distributed in the range of 2-40 nm.
The cathode material ZnAl of the invention2O4the/C can be used for the negative pole piece of the lithium ion battery, and comprises the following components in percentage by mass of 100 percent: active material ZnAl2O470-90% of/C, 5-20% of conductive carbon black and 5-10% of binder; more preferably, ZnAl2O4and/C, uniformly mixing the conductive carbon black and the binder in a mass fraction ratio of 7:2:1, and using the mixture to manufacture a negative pole piece.
The electrolyte in the lithium ion battery adopts liquid electrolyte, and the solvent is mainly one or more of propylene carbonate, dimethyl carbonate, ethylene carbonate, methyl ester and ethyl methyl carbonate; the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate and lithium trifluoromethanesulfonate. Wherein the molar concentration of the lithium salt is 0.5-2 mol/L.
The lithium ion battery provided by the invention uses the anode material and the electrolyte formula. Due to ZnAl2O4the/C has large specific surface area and abundant pores, promotes the penetration of electrolyte and shortens Li+The pores are ZnAl in the charge-discharge process2O4The volume expansion of the lithium ion battery plays a role in buffering, so that the battery has high coulombic efficiency, good stability and excellent rate performance.
The invention has the beneficial effects that:
hair brushA ZnAl material for lithium ion battery2O4a/C negative electrode material and its use. The ZnAl2O4the/C negative electrode material has the advantages of high safety, high coulombic efficiency, good cycling stability, excellent rate capability and the like; the obtained lithium ion battery ZnAl2O4the/C cathode material is simple to prepare, green and environment-friendly, has mild reaction conditions, greatly reduces the preparation time and the process cost, and has great potential application value.
Description of the drawings:
FIG. 1 shows ZnAl obtained in example 1 of the present invention2O4FESEM pictures (a-d), elemental plane scans (e) of/C samples;
FIG. 2 shows ZnAl obtained in example 1 of the present invention2O4Transmission Electron Microscopy (TEM) image (a), High Resolution Transmission Electron Microscopy (HRTEM) image (b, C) and Selected Area Electron Diffraction (SAED) image (d) of/C sample;
FIG. 3 shows ZnAl obtained in example 1 of the present invention2O4An XPS energy spectrum full spectrum (a), a C1 s spectrogram (b), an O1 s spectrogram (C), an Al 2p spectrogram (d) and a Zn 2p spectrogram (e) of the/C sample;
FIG. 4 shows Al obtained in example 1 of the present invention3+/Zn2+-TA precursor and ZnAl2O4An infrared spectrum of the/C composite material;
FIG. 5 shows ZnAl obtained in example 1 of the present invention2O4Raman spectrum of the/C sample;
FIG. 6 shows ZnAl obtained in example 1 of the present invention2O4Thermogravimetric plot of/C sample;
FIG. 7 shows ZnAl obtained in example 1 of the present invention2O4Adsorption-desorption isotherm curve (a) and pore size distribution curve (b) for the/C sample;
fig. 8 is a cyclic voltammogram of the initial five cycles of the lithium ion battery obtained in example 2 of the present invention;
fig. 9 is a charge-discharge curve diagram of the lithium ion battery obtained in example 2 of the present invention;
fig. 10 is a cycle performance test chart of the lithium ion battery obtained in example 2 of the present invention at different current densities;
fig. 11 is a rate performance test chart of the lithium ion battery obtained in example 2 of the present invention;
FIG. 12 shows a lithium ion battery obtained in example 2 of the present invention and a lithium ion battery prepared by using ZIF-8, ZIF-8/TA and ZIF-8/Al, respectively3+An electrochemical ac impedance diagram (a) and a cycle performance diagram (b) of a lithium ion battery as a negative electrode.
The specific implementation mode is as follows:
the invention provides ZnAl2O4and/C material and lithium ion battery using the same as negative electrode material. Active material ZnAl2O4the/C is synthesized by normal temperature preparation and heat treatment.
The electrolyte is liquid electrolyte, the solvents are ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, the solute is lithium hexafluorophosphate, the molar concentration of lithium salt is 0.5-2 mol/L, and a small amount of lithium pieces are required to be placed before the electrolyte is used to remove moisture in the electrolyte.
The assembly process of the button cell is completed in a vacuum glove box filled with argon, the oxygen content and the water content of the button cell are both less than 0.1 ppm, a lithium metal sheet is used as a counter electrode, and a cell diaphragm is a polypropylene diaphragm of Shenzhen, Kezhida science and technology Limited.
The invention is further illustrated by the following figures and examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adjustments to the present invention based on the above disclosure and still fall within the scope of the present invention.
Example 1:
this example shows a porous ZnAl structure2O4A method for synthesizing a/C negative electrode material. ZnAl2O4the/C negative electrode material is prepared at normal temperature and synthesized by heat treatment, and comprises the following steps:
(1) 2.97 g of zinc nitrate hexahydrate and 2.46 g of 2-methylimidazole were poured into 50 mL of a methanol solution, and sufficiently dissolved by sonication. Thereafter, the methanol solution containing 2-methylimidazole was slowly poured into the methanol solution containing zinc nitrate hexahydrate. The resulting mixed solution was stirred at 600 rpm for 24 hours at room temperature. Finally, ZIF-8 white powder was obtained by centrifugation, washed with methanol several times, centrifuged, and dried in an oven at 60 ℃.
(2) 0.28 g of aluminum trichloride hexahydrate was sufficiently dissolved in 20 mL of ultrapure water, and mixed with 20 mL of a tannic acid solution (10 mg/mL), and after stirring at room temperature for 2 hours, 0.28 g of ZIF-8 white powder was added, and after further stirring for 1 hour, a flocculent precipitate appeared in the solution. Then, the precipitate was washed with ultrapure water several times and centrifuged, and the obtained sample was dried in an oven at 60 ℃ and recorded as Al3+/Zn2+-a TA precursor.
(3) Taking a proper amount of the precursor in a square boat, directly heating to 600 ℃ at a constant heating rate (5 ℃/min) in a pure nitrogen atmosphere, and keeping the temperature for 4 h. After the temperature reduction is finished, the ZnAl for the lithium ion battery can be obtained2O4a/C negative electrode material.
FIG. 1 is ZnAl2O4FESEM image of/C sample, elemental plane scan. As can be seen, ZnAl2O4the/C composite material has rich porous structure and different pore sizes, can increase the specific surface area of the material, is favorable for the permeation of electrolyte, increases the contact area between the electrolyte and an electrode material, and can improve Li+The transmission rate of (c). From this it can also be observed that ZnAl2O4the/C composite material has rough surface and particle adhesion, which is caused by CO generated in the calcining process2、H2O, etc. To further understand ZnAl2O4The distribution of each element in the/C composite material is subjected to element scanning, and the Zn, Al, O and C elements are uniformly distributed on the material.
FIG. 2 is ZnAl2O4Transmission Electron Microscopy (TEM), High Resolution Transmission Electron Microscopy (HRTEM) and Selected Area Electron Diffraction (SAED) images of/C samples. As can be seen from the figure, the material has a large number of pores, which indicates that ZnAl exists2O4The composite material has a rich porous structure ofLi+The de-intercalation process increases active sites, improves the electrochemical performance of the active sites as LIBs cathode materials, and ZnAl2O4The nano particles are grown in the carbon-based material calcined by the ZIF-8, so that the agglomeration phenomenon of the nano particles can be effectively relieved. The lattice fringe spacing of about 0.24 nm and 0.28 nm can be obtained from a high-resolution transmission electron microscope image and is respectively matched with ZnAl2O4The (311) and (220) crystal planes of the nanoparticles correspond to each other, which is consistent with the X-ray powder diffraction (XRD) analysis result, indicating that ZnAl is successfully prepared2O4And (3) nanoparticles. As can be seen from the selected area electron diffraction pattern, the material has a polycrystalline structure and can well react with ZnAl2O4The (220), (311) and (422) crystal planes of the nanoparticles correspond.
FIG. 3 is ZnAl2O4An XPS energy spectrum full spectrum (a), a C1 s spectrum (b), an O1 s spectrum (C), an Al 2p spectrum (d) and a Zn 2p spectrum (e) of the/C sample. As can be seen from the figure, the characteristic peaks at the electron binding energies of 284.82 eV and 287.85 eV correspond to the C-C bond and the C = O bond, respectively, and the characteristic peak at 532.22 eV in the O1 s spectrum represents the carbon-oxygen bond position, indicating that ZnAl after calcination in a nitrogen atmosphere at 600 ℃ is formed2O4the/C composite still has active functional groups. The characteristic peak appearing at 74.32 eV in the Al 2p spectrum indicates that Al3+Is present. The peaks at 1044.98 eV and 1021.96 eV in the Zn 2p spectrum of graph (e) represent Zn, respectively2+Zn 2p of1/2And Zn 2p3/2. The above conclusion illustrates ZnAl2O4The presence of the/C composite material.
FIG. 4 is Al3+/Zn2+-TA precursor and ZnAl2O4Infrared spectrogram of the/C composite material. 1689.8 cm-1The absorption peak at (A) is due to the stretching vibration of the C = O bond, 1580.4 cm-1Absorption peak of (b) corresponds to COO-At 1498.4 cm-1The peak of (2) may be related to the vibration of the N-H bond, and the stretching vibration of the C-C bond corresponds to the absorption peak at 1437.7, 1352.8 cm-1The absorption peak is due to NO3-Caused by antisymmetric telescopic vibration of 1310.4 and 1198.5 cm-1The peaks at (A) respectively correspond toIs on CH2Torsional vibration and C-N stretching vibration of 1069.8 and 1037.1 cm-1The absorption peaks corresponding to C-O bond stretching vibration at 834.1 and 751.1 cm-1The absorption peak at (A) may be related to the benzene ring pair disubstituted and C-H bending vibration. ZnAl2O4The ir spectrum of the/C composite is comparable to that described above, with most of the functional groups lost after calcination, leaving almost only weak absorption peaks for C-O and C = O bonds.
FIG. 5 is ZnAl2O4Raman spectrum of the/C sample. The ratio of the D peak (10659.12) to the G peak (12116.96) is 0.8797, which shows that the carbon matrix is mainly ordered carbon layer, the graphitization degree is high, and ZnAl is improved2O4the/C composite material is used as the conductivity of the negative electrode of the lithium ion battery.
FIG. 6 is ZnAl2O4Thermogravimetric plot of the/C sample under nitrogen atmosphere. It can be seen that the first plateau of mass loss, which occurs in the temperature range of 25 c to 600 c, is mainly due to free water adhering to the inter-particle and pore channels, and that part of the organic matter is pyrolyzed and carbonized, with a mass loss rate of about 7.9%. After 600 ℃, the mass of the material starts to decrease gradually until it is almost constant at a temperature of 900 ℃, in which temperature range ZnAl is present2O4Gradually increases in crystallinity. ZnAl is obtained by analysis2O4The carbon content in the/C composite was approximately 30.7%.
FIG. 7 is ZnAl2O4Adsorption and desorption isotherms and pore size distribution curves of the/C sample. As can be seen from the figure, the nitrogen adsorption and desorption isotherm curve of the sample belongs to a typical type IV isotherm curve, which indicates that ZnAl2O4the/C composite material is mainly mesoporous, and the appearance of large pores is formed by the accumulation of powder. ZnAl2O4The BET specific surface area of the/C composite material is 274.83 m2 g-1Pore volume of 0.5558 cm3 g-1. At P/P0Is 0.8 due to ZnAl2O4the/C composite material is subjected to capillary condensation, the isotherm rises rapidly, and the isothermal curve obtained in desorption is just caused by the capillary condensationThe line does not coincide with the isothermal curve obtained during adsorption, i.e., adsorption hysteresis occurs, resulting in a hysteresis loop. The pore diameter is mainly distributed in the range of 2-40 nm, and the abundant mesopores are mainly derived from the original pore structure of ZIF-8 and the pores formed under the action of TA. Therefore, the large specific surface area and the abundant pores facilitate the penetration of the electrolyte, shortening Li+The pores are ZnAl in the charge-discharge process2O4The volume expansion of the catalyst plays a role in buffering, and the ZnAl is improved2O4Stability of the/C composite as a negative electrode for LIBs.
Example 2:
this example shows a porous ZnAl structure2O4and/C is a lithium ion battery with a negative electrode.
Preparing electrode slurry according to the proportion of 7:2:1 (sample: conductive carbon black: PVDF (polyvinylidene fluoride)), wherein the conductive carbon black is Super P, the binder is 5% PVDF, namely 1.0 g of polyvinylidene fluoride powder is fully dissolved in 19.0 g of N-methyl pyrrolidone (NMP) solvent, and then the electrode slurry is stored in a dark place.
Weighing 70 mg of the sample prepared in the example 1, adding about 20 mg of Super P, placing the mixture in a mortar, forcibly grinding the mixture for 15 to 20 min to ensure that the particles are uniform in size, fully mixing the particles, and then drying the mixture in an oven at 60 ℃; then, taking out and weighing the dried mixed sample, and mixing the obtained product according to the weight ratio of the anode active material: conductive carbon black: binder = 7:2:1(wt%：wt%：wt%) The mass ratio of the components is that a certain amount of 5 percent PVDF is dripped into a small weighing bottle and stirred at the rotating speed of 700 rpm, the stirred slurry is evenly coated on the surface of copper foil by a spoon after being evenly stirred, and the loading amount of active substances is controlled to be about 1-2 mg/cm by controlling the coating thickness by an applicator2. After the coating was completed, the copper foil was quickly transferred to a vacuum oven at 80 ℃ and continuously dried for 12 hours. And then cutting the prepared electrode plate into small round pieces with the diameter of 10 mm by using a sheet punching machine, quickly weighing the small round pieces, and putting the weighed electrode plate into a vacuum oven at the temperature of 80 ℃ again for 10 hours. When cooled to room temperature, was quickly transferred to a glove box for use.
The electrolyte is liquid electrolyte, solvents are ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate, solute is lithium hexafluorophosphate, the molar concentration of lithium salt is 1 mol/L, and a small amount of lithium pieces are required to be placed before the electrolyte is used to remove moisture in the electrolyte.
The prepared ZnAl is put into2O4The button cell is assembled by the/C negative pole piece, the electrolyte, the metal potassium piece and other materials such as a diaphragm, a gasket, an elastic piece, a cell shell and the like. Before the electrochemical test of the button cell, the button cell needs to be kept stand for 12 hours to enable the electrolyte to fully soak the pole piece.
Performing cyclic voltammetry on the battery obtained in the embodiment, wherein the scanning voltage interval is 0.01-3V and the scanning rate is 0.1 mV/s during the test; constant current charge-discharge test is carried out, and the voltage window is 0.01-2.5V.
Fig. 8 is a cyclic voltammetry graph of the initial 5 cycles of the lithium ion battery obtained in example 2 of the present invention, and it can be seen from the graph that a weak reduction peak appears in a voltage range of 1.2-1.5V in the first cathode scan, which may be due to decomposition of the liquid electrolyte to form a solid electrolyte membrane. Immediately after 0.624V, a higher reduction peak occurs, in which case Zn2+And Al3+Is reduced into metal Zn and Al to generate Li2O, and there is a high possibility that the decomposition of the liquid electrolyte to produce a solid electrolyte membrane occurs simultaneously, but the peak does not appear at the cathode scan thereafter, indicating ZnAl2O4Is irreversible. During the first anode scanning, a weak oxidation peak appears in the voltage range of 1.0-1.3V, and then metal Zn and Al are oxidized to generate ZnO and Al2O3And the peak appears to be slightly shifted in position toward the high potential direction as compared with the results of the following four scans because Li occurs during the first cycle of scanning+The reversible deintercalation process of (A) makes ZnAl2O4the/C electrode material produces a slight structural adjustment, improving the electrical contact between the electrode material and the current collector and electrolyte. In addition, the area formed by 2 to 5 rounds of scanning is significantly reduced compared to the first round due to the formation of a stable SEI film and Li+Unavoidable Li in the deintercalation process+And (4) loss. Watch withAs can be seen from the inspection of the graph, except the first scanning curve, the other four scanning curves are basically overlapped and do not change any more, which shows that ZnAl2O4the/C electrode material has good cycle performance in the charge and discharge processes.
Fig. 9 is a graph of the initial 5-cycle charge and discharge curve of the lithium ion battery obtained in example 2 of the present invention at a current density of 200 mA/g, and it can be seen that two turning points appear in the initial discharge curve around the voltage values of 1.5V and 0.65V. Wherein, the turning point appearing around 1.5V corresponds to the wide reduction peak appearing at the place in the CV curve of FIG. 8, the voltage value slowly decreases around 0.65V, and then ZnAl2O4A reduction reaction occurs, i.e., formula (4-1), Li+The amount of embedding in the crystal is increasing. However, the inflection point at 0.65V is deviated from the cell potential value of the reduction peak at 0.624V as shown in the CV curve of fig. 8, which may be caused by a difference in the degree of polarization of the cell due to the difference in the current of the cyclic voltammetry test and the charge-discharge test. Except the first charge-discharge curve, the other four charge-discharge curves are basically overlapped, which shows that ZnAl2O4the/C composite material has good cycle stability as the cathode of the lithium ion battery, and the cycle stability is matched with that of ZnAl2O4The analysis result of the cyclic voltammetry curve of the/C electrode material is consistent. ZnAl2O4The first charging and discharging specific capacities of the/C electrode are 1983.16 mAh/g and 1028.71 mAh/g respectively, the initial coulombic efficiency is 51.87%, the discharging specific capacities of the rest 2-5 circles are 999.77 mAh/g, 967.47 mAh/g, 949.14 mAh/g and 940.36 mAh/g in sequence, and the coulombic efficiencies are 95.51%, 96.59%, 97.24% and 97.81% in sequence, and the coulombic efficiency after the first charging and the discharging specific capacities are close to 100% continuously. The reason for irreversible capacity loss is mainly attributed to: (1) the structure of the electrode material will be destroyed to some extent during the de-intercalation process, and the resulting structural destruction is not repairable during the subsequent charging and discharging processes, while Li is first intercalated+The amount of Li cannot be totally deintercalated, resulting in Li+Irreversible loss of (a); (2) in the charging and discharging process, the active substances are agglomerated, the electric contact between the electrode material and the current collector and between the electrode material particles is reduced, and lithium is enabled to be containedThe capacity of the ion battery is reduced; (3) the decomposition of the electrolyte to form a solid electrolyte membrane consumes a portion of Li+Causing irreversible capacity loss.
Fig. 10 is a cycle performance test chart of the lithium ion battery obtained in example 2 of the present invention at different current densities. ZnAl after 250 cycles under the current density of 200 mA/g2O4the/C negative electrode can still provide high specific discharge capacity of 755.08 mAh/g, and the initial coulombic efficiency is 51.87%. Among them, the specific capacity degradation of 1 to 4 turns is relatively severe because a part of Li is consumed in the process that the electrolyte is decomposed to form the solid electrolyte membrane+The irreversible capacity loss is caused, after that, the capacity attenuation becomes slow, the coulombic efficiency approaches 100 percent gradually, which shows that a stable SEI film is formed, the irreversible capacity loss caused by the first charge and discharge is not counted, the capacity retention rate is 75.57 percent, and the specific discharge capacity of each cycle loss is 0.98 mAh g-1Per turn; in addition, it is also directed to ZnAl2O4The cycle performance of the/C electrode under high current density is tested. ZnAl at a current density of 500 mA/g2O4The first discharge capacity and the first charge specific capacity of the/C electrode are 2144.06 mAh/g and 732.13 mAh/g respectively, and ZnAl is firstly used2O4The specific capacity of the/C electrode is gradually reduced and gradually increased after 150 circles, the specific discharge capacity of 431.28 mAh/g is provided in the 500 th charging and discharging, the capacity retention rate is 45.77%, and the specific discharge capacity of each cycle loss is 1.02 mAh/g/circle; under the current density of 1.0A/g, the discharge specific capacity of 209.77 mAh/g is provided after 1000 times of circulation, and the discharge specific capacity of each circulation loss is 0.42 mAh/g/ring; visible ZnAl2O4the/C electrode material has excellent cycle stability.
Fig. 11 is a rate capability test chart of the lithium ion battery obtained in example 2 of the present invention. As can be seen from the figure, when the current density is increased from 200 mA/g to 1000 mA/g, the discharge specific capacity at the corresponding 10 th circle is 748.44, 655.57, 607.62, 573.82 and 544.72 mAh/g in sequence, and then the current density is reduced to 200 mA/g, at this time, the discharge specific capacity at the 10 th circle is 722.51 mAh/g, and the specific capacity at the current density of 200 mA/g for the first time is compared with that at the current density of 200 mA/gThe values are approximately coincident, indicating ZnAl2O4The good rate capability of the/C electrode is probably attributed to the improvement of ZnAl after the carbonization of TA and ZIF-82O4The conductivity of the/C electrode material. The electrodes were then also tested at current densities of 400, 800 and 200 mA/g, with specific discharge capacities at turn 10 of 647.13, 560.00 and 700.04 mAh/g in that order, with a slight decrease in the capacity values compared to the previous capacity values at the same current densities, probably due to ZnAl2O4The structure of the/C electrode is damaged to a certain extent in the charging and discharging processes, so that the capacity is reduced.
FIG. 12 shows a lithium ion battery obtained in example 2 of the present invention and a lithium ion battery prepared by using ZIF-8, ZIF-8/TA and ZIF-8/Al, respectively3+Electrochemical alternating current impedance diagram and cycle performance diagram of the lithium ion battery as the cathode. As can be seen from the figure, ZIF-8/TA, ZIF-8/Al3+And ZnAl2O4Charge transfer resistance R of/C electrode material2690.9, 644.3, 942.7 and 440.7 Ω sequentially, and the specific discharge capacity of the material after charging and discharging for 100 times under the current density of 200 mA/g is 347.39, 508.46, 192.93 and 811.28 mAh/g respectively, and the observation of a Nyquist diagram shows that ZIF-8/TA and ZnAl in a low-frequency region2O4The slopes of the/C slope portions are all larger than those of ZIF-8 and ZIF-8/Al3+The above results show that the introduction of TA reduces the charge transfer resistance and lithium ion diffusion resistance of the electrode material. Calculating to obtain ZnAl2O4The exchange current density of the/C electrode material is 7.28 multiplied by 10-3 mA∙cm-2And has excellent electrode dynamics.
The embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above embodiments, and any modification, equivalent replacement, or improvement made by those skilled in the art within the spirit and principle of the present invention should be within the protection scope of the present invention.

Claims (4)

1. A porous carbon-based negative electrode material of zinc aluminate solid solution for a lithium ion battery is characterized in that: the negative electrode material is ZnAl2O4Composite material/C。
2. A method for preparing the porous carbon-based negative electrode material of zinc aluminate solid solution for lithium ion batteries according to claim 1, characterized in that: the method comprises the following steps:
(1) respectively pouring zinc nitrate hexahydrate and 2-methylimidazole into a methanol solution, performing ultrasonic treatment to fully dissolve the zinc nitrate hexahydrate and the 2-methylimidazole, slowly pouring the methanol solution containing the 2-methylimidazole into the methanol solution containing the zinc nitrate hexahydrate, stirring the obtained mixed solution at the rotating speed of 600 rpm for 24 hours at room temperature, centrifuging to obtain ZIF-8 white powder, washing and centrifuging for multiple times by using methanol, and drying in an oven at 60 ℃;
(2) dissolving aluminum trichloride hexahydrate in ultrapure water, mixing with a tannic acid solution, stirring for 2 hours at room temperature, adding ZIF-8 white powder obtained in the step (1), stirring for 1 hour, washing and centrifuging the precipitate for multiple times by using ultrapure water after flocculent precipitate appears in the solution, and drying the obtained sample in a 60 ℃ oven to obtain Al3+/Zn2+-a TA precursor;
(3) taking Al3+/Zn2+And (4) treating the TA precursor in the ark at high temperature in a pure nitrogen atmosphere, and cooling to obtain the porous carbon-based negative electrode material of the zinc aluminate solid solution for the lithium ion battery.
3. A method of manufacturing as claimed in claim 2, wherein: the high-temperature treatment in the step (3) is specifically that the temperature is directly increased to 600 ℃ at a constant temperature increase rate of 5 ℃/min, and the temperature is kept for 4 hours.
4. The use of the porous carbon-based negative electrode material of zinc aluminate solid solution for lithium ion battery as defined in claim 1, wherein: the lithium ion battery negative pole piece comprises the following components in percentage by mass of 100%: active material ZnAl2O470-90% of/C, 5-20% of conductive carbon black and 5-10% of binder.
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