CN107331853B - Graphene composite multilayer porous spherical lithium manganate electrode material and lithium ion battery prepared from same - Google Patents
Graphene composite multilayer porous spherical lithium manganate electrode material and lithium ion battery prepared from same Download PDFInfo
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
The invention discloses a graphene composite multilayer spherical lithium manganate electrode material capable of charging and discharging lithium ions and a high-voltage chargeable and dischargeable lithium ion battery comprising the same. The multilayer porous spherical lithium manganate is prepared by taking manganese sesquioxide as a precursor by using a solid phase method, has the shapes of multiple holes, layering and openings, and the graphene lamellar structure in the compounded material is uniformly dispersed around the prepared lithium manganate particles. The high-voltage chargeable and dischargeable lithium ion battery takes graphene composite multilayer spherical lithium manganate with holes as a positive electrode, metal lithium or an embeddable lithium active material as a negative electrode, and a soluble lithium salt organic solution as an electrolyte. The graphene composite multilayer porous spherical lithium manganate serving as the lithium ion battery electrode material has the advantages of low cost, rich raw materials, high voltage, good rate capability and strong cycle stability. The chargeable and dischargeable lithium ion battery containing the material has high energy density and high power density and has wide market application prospect.
Description
Technical Field
The invention belongs to the field of lithium ion battery anode materials, and particularly relates to a graphene composite multilayer porous spherical lithium manganate electrode material capable of charging and discharging lithium ions and a high-voltage chargeable and dischargeable lithium ion battery comprising the same.
Background
Lithium ion batteries are used as a medium for energy transmission between new energy sources and electronic devices, and have been widely used in devices such as mobile phones, computers, electric vehicles, and the like due to their advantages of high specific energy, long cycle life, and the like. However, in the next generation of transportation, power grid, and higher-demand consumer electronics, the current lithium ion battery cannot meet the demand, and therefore, the development of a lithium ion battery with high voltage, high power density, and high energy density is an urgent need.
In a lithium ion battery system, the influence of the positive electrode material on the battery performance is the most obvious. Compared with lithium cobaltate, lithium manganese phosphate and ternary materials, spinel lithium manganate has the advantages of rich manganese source, stable and simple synthesis process, high voltage, low cost, good safety and the like, is successfully applied to the production of lithium ion batteries, but the further application of spinel lithium manganate is greatly limited by poor rate performance and short cycle life. Due to the dissolution of Mn in an electrochemical reaction, the spinel lithium manganate has poor cycling stability of the material; and in large multiplying power, the lithium ion transmission rate and the electronic conductivity of the material are lower, so that the material is seriously polarized under large multiplying power, and the specific discharge capacity is lower.
Today, the above problems are mainly solved by controlling morphology, bulk doping and material compounding. In the aspect of morphology control, the material is nanocrystallized, a porous accumulation structure is constructed, and the ion transmission rate is improved. In addition, electron conductivity is improved by compounding with a highly conductive material such as carbon. However, the activity of the nano material is too high, so that the dissolution of the material is accelerated, the stability is reduced, and the cycle performance and the multiplying power of the element-doped lithium manganate cannot be obviously improved.
Disclosure of Invention
The patent discloses a compound multilayer of graphite alkene foraminiferous type spherical lithium manganate of graphite alkene has novel unique appearance and even graphite alkene cladding: the appearance of the porous layered opening increases the storage space of the electrolyte and shortens Li+The concentration polarization is reduced by the transmission path, and the ion diffusivity and the cycle performance of the material are successfully improved; the multilayer porous spherical lithium manganate is composed of a polyhedral crystal structure, so that the dissolution of Mn is effectively reduced, and the cycling stability of the material is enhanced; graphite (II)The uniform dispersion and coating of the alkene enhance the electronic conductivity of the material. Therefore, the material has the advantages of low cost, rich raw materials, high voltage, good rate capability and strong cycle stability, and the rechargeable lithium ion battery containing the material has high energy density and high power density and has wide market application prospect.
The technical scheme for realizing the invention is as follows: the utility model provides a graphite alkene compound multilayer foraminiferous spherical lithium manganate electrode material, graphite alkene compound multilayer foraminiferous spherical lithium manganate electrode material comprises around lithium manganate granule by lamellar structure's graphite alkene homodisperse, lithium manganate piles up the multilayer foraminiferous spherical structure that forms for primary particle, and the particle diameter of primary particle is 100 plus one's blood sugar 200 nm, and the particle diameter of the multilayer foraminiferous spherical lithium manganate electrode material that piles up and forms is 1-5 mu m.
The amount of graphene in the graphene composite multilayer spherical lithium manganate electrode material is 1-20% of the mass of lithium manganate.
The preparation method of the graphene composite multilayer porous spherical lithium manganate electrode material comprises the following steps:
(1) dissolving cetyl trimethyl ammonium bromide and ammonium bicarbonate in deionized water to form a mixed solution I;
(2) dissolving manganese sulfate in deionized water to form a mixed solution II;
(3) placing the mixed solution I obtained in the step (1) in an oil bath at the temperature of 40-60 ℃, dropwise adding the mixed solution II obtained in the step (2) into the mixed solution I, and adjusting the pH value to be 7-8 after dropwise adding to obtain a turbid solution;
(4) washing the turbid solution obtained in the step (3) with water, centrifuging, and drying to obtain manganese carbonate primary powder, wherein the manganese carbonate primary powder is calcined at the temperature of 600-800 ℃ to obtain a precursor manganese sesquioxide;
(5) adding the precursor manganous oxide and lithium salt obtained in the step (4) into absolute ethyl alcohol for grinding, and placing the mixture in a tubular furnace with an oxygen atmosphere for 500- & 600- & gtoC, after pre-burning for 2-6h, heating to 600-800 ℃ for calcining for 8-15 h to obtain multilayer porous spherical lithium manganate;
(6) and (3) dispersing graphene in deionized water, adding the multilayer porous spherical lithium manganate obtained in the step (5), stirring, centrifuging and drying to obtain the graphene composite multilayer porous spherical lithium manganate electrode material.
The mass ratio of the hexadecyl trimethyl ammonium bromide to the ammonium bicarbonate to the water in the step (1) is 1: (40-50): 1000, parts by weight; the mass ratio of manganese sulfate to water in the step (2) is 1: 80-100 parts of; the molar ratio of the precursor manganese sesquioxide and the lithium salt in the step (5) is 8-10: 1.
the lithium ion battery prepared from the graphene composite multilayer porous spherical lithium manganate electrode material mainly comprises a positive plate, a negative plate, electrolyte, a diaphragm and a shell, the lithium ion battery adopts the graphene composite multilayer porous spherical lithium manganate electrode material as a positive electrode material, adopts metal lithium or an embedded and removable lithium active material as a negative electrode material, the diaphragm is a polyethylene, polypropylene microporous membrane, glass fiber diaphragm or various composite diaphragms thereof, and a soluble lithium salt organic solution is the electrolyte.
The lithium ion battery cathode material prepared from the graphene composite multilayer porous spherical lithium manganate electrode material is metallic lithium or an embeddable lithium active material, and comprises a carbon material or a titanium-based material and a composite material thereof.
The soluble lithium salt organic solution is obtained by dissolving lithium salt in an organic solvent, wherein the lithium salt is lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium tetrafluoroborate (LiBF)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium bis (trifluoromethylsulfonyl) imide (LiN (CF)3SO2)2) The organic solvent is one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dimethyl ether (DME) and Tetrahydrofuran (THF).
The conductive agent of the lithium ion battery is acetylene black, carbon black or graphite, the binder is polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, polyacrylic acid or styrene butadiene rubber, and the dispersant is water, ethanol, isopropanol or 1-methyl-2-pyrrolidone.
The positive plate and the negative plate of the lithium ion battery are prepared by filling slurry obtained by uniformly mixing the conductive agent, the binder and the dispersing agent on a current collector.
The current collector is made of carbon cloth, metal stainless steel, nickel and aluminum porous, net or film materials.
The shell of the lithium ion battery is made of organic plastics, an aluminum shell, an aluminum plastic film (a soft package battery), stainless steel and composite materials thereof.
The shape of the lithium ion battery can be button type, column type or square type.
The invention has the beneficial effects that: the method has the advantage that the graphene composite multilayer porous spherical lithium manganate is used as the anode material. The particle size of the material is 1-5 mu m, the material is formed by stacking 100-plus-200 nm primary particles, the material has the appearance of being porous, layered and open, and the graphene lamellar structure is uniformly dispersed around the lithium manganate, so that the diffusion rate of electrons and ions in the material can be obviously improved, the electrochemical stability is enhanced, further, the lithium ion battery with low cost, rich raw materials, high voltage, good rate capability and strong cycle stability is obtained, and the power and energy density of the material are improved. The electrode material has the advantages of low price, safety, environmental friendliness and the like, and the rechargeable lithium ion battery containing the material has high energy density and high power density and wide market application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an X-ray diffraction (XRD) pattern of the multilayer porous spheroidal lithium manganate prepared in example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the multilayer porous spheroidal lithium manganate prepared in example 1.
Fig. 3 is an SEM image of the graphene composite multilayer porous spheroidal lithium manganate prepared in example 1.
Fig. 4 is a charge-discharge curve diagram of the lithium ion battery in example 1.
Fig. 5 is a graph of rate performance of the lithium ion battery in example 1.
Fig. 6 is a graph of the cycle performance of the lithium ion battery in example 1.
Fig. 7 is a graph showing the charge and discharge curves of the lithium ion battery in example 2.
Fig. 8 is a charge-discharge curve diagram of the lithium ion battery in example 3.
Fig. 9 is a graph showing the charge and discharge curves of the lithium ion battery in example 4.
Fig. 10 is a graph showing the charge and discharge curves of the lithium ion battery in example 5.
Fig. 11 is a graph showing the charge and discharge curves of the lithium ion battery in example 6.
Fig. 12 is a graph showing the charge and discharge curves of the lithium ion battery in example 7.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The synthesis steps of the graphene composite multilayer porous spherical lithium manganate used by the invention are as follows: 0.25g of cetyltrimethylammonium bromide (CTAB) and 11.85 g of ammonium bicarbonate were weighed out and dissolved in 250mL of deionized water to form a first mixed solution, and 2.54g of manganese sulfate was weighed out and dissolved in 250mL of deionized water to form a second mixed solution. Adding the second mixed solution into the first mixed solution dropwise for 30min in 50 deg.C oil bath, adjusting pH to 7.5, maintaining constant pH in the oil bath for 30min, standing for one day to obtain turbid solutionWashing with water, centrifuging, and drying in a 60 ℃ oven to obtain the manganese carbonate primary powder. And calcining the primary powder in a muffle furnace at 710 ℃ to obtain a precursor manganese sesquioxide. 0.084 g of LiOH. H was taken2Placing O and 0.3g of manganese sesquioxide in a mortar, taking 1mL of absolute ethyl alcohol as a solvent, grinding uniformly, transferring to a porcelain cup, placing in a tube furnace in an oxygen atmosphere, presintering for 4h at 560 ℃, heating to 750 ℃, and calcining for 10h to obtain the multilayer porous spherical lithium manganate. And then, weighing 5 wt% of graphene, dispersing the graphene in 50mL of deionized water, performing ultrasonic treatment for 1 h, adding multilayer porous spherical lithium manganate powder, stirring for 4h, and performing centrifugal drying to obtain the multilayer porous spherical lithium manganate with composite graphene.
FIG. 1 is an X-ray diffraction (XRD) diagram of multilayer porous spherical lithium manganate, which corresponds to a standard card of spinel lithium manganate and has good crystallinity, FIG. 2 is a Scanning Electron Microscope (SEM) diagram of multilayer porous spherical lithium manganate, which is a secondary structure formed by stacking of 100-200 nm small particles; FIG. 3 is an SEM image of multilayer porous spherical lithium manganate after graphene is compounded, wherein graphene is about 1 μm lamellar particles and is uniformly dispersed on the lithium manganate particles.
Taking the prepared graphene composite multilayer porous spherical lithium manganate material as a positive electrode active material, wherein the weight ratio of the positive electrode material to acetylene black and polyvinylidene fluoride is 80:10: mixing at a mass ratio of 10, adopting 1-methyl-2-pyrrolidone as a dispersing agent, uniformly mixing the mixture, mixing into slurry, coating the slurry on an aluminum foil, drying at 60 ℃, cutting to obtain a positive pole piece, adopting a lithium piece as a negative pole (the negative pole capacity is far greater than the capacity of the cut positive pole piece), separating the positive pole piece and the lithium piece by adopting a Celgard 2500 type polypropylene microporous membrane, and adopting 1M LiPF6Dissolution in EC: the lithium ion battery assembled in the above process is subjected to charge and discharge tests at room temperature in a potential range of 3.0V-4.5V, and the charge and discharge curve, rate performance and cycle performance of the lithium ion battery are shown in fig. 4, 5 and 6. The discharge capacity of the discharge platform under 1C is about 4V, and under the multiplying power of 50C, the discharge specific capacity can reach 110 mAh/g, 10C timesThe material still maintained a capacity of 114.7 mAh/g after 400 weeks cycling at this rate.
Example 2
The preparation of the graphene composite multilayer porous spherical lithium manganate material of the embodiment is the same as that of embodiment 1.
The prepared graphene composite multilayer porous spherical lithium manganate material is used as a positive electrode active material, commercial graphite is used as a negative electrode active material, and the ratio of the positive electrode active material to the negative electrode active material to acetylene black to polyvinylidene fluoride is 80:10: mixing at a mass ratio of 10, adopting 1-methyl-2-pyrrolidone as a dispersing agent, uniformly mixing the mixture, mixing into slurry, respectively coating the slurry on an aluminum foil and a copper foil, drying at 60 ℃, cutting to obtain a corresponding positive pole piece and a corresponding negative pole piece (the negative pole capacity is far greater than the capacity of the cut positive pole piece), separating the pole pieces from the lithium pieces by adopting a Celgard 2500 type polypropylene microporous membrane, and using 1M LiPF6Dissolution in EC: the lithium ion battery assembled in the process is subjected to constant current charge and discharge test at a constant current multiplying power of 1C within a potential range of 2.8-4.5V at room temperature, a discharge platform is about 3.65V, and a test result shows that the specific discharge capacity of the battery is 113mAh/g, and a charge and discharge curve of the battery is shown in figure 7.
Example 3
The graphene composite multilayer porous spherical lithium manganate material prepared in example 1 is used as a positive electrode active material, and the ratio of the positive electrode material to acetylene black and polyvinylidene fluoride is 80:10: mixing at a mass ratio of 10, adopting 1-methyl-2-pyrrolidone as a dispersing agent, uniformly mixing the mixture to prepare slurry, coating the slurry on an aluminum foil, drying at 60 ℃, cutting to obtain a positive pole piece, adopting a lithium piece as a negative pole (the capacity of the negative pole is far greater than that of the cut positive pole piece), separating the positive pole piece and the lithium piece by adopting a whatman glass fiber diaphragm, and adopting 1 MLiPF6Dissolution in EC: and (2) DMC (mass ratio of 1: 1) is used as electrolyte, a stainless steel shell is used as a shell, and the CR2025 type button cell is assembled, wherein the lithium ion battery assembled in the process is subjected to charge and discharge tests at 0.5C multiplying power within a potential range of 3.0V-4.5V at room temperature. The test result shows that the specific discharge capacity of the battery is 135 mAh/gThe charge and discharge curves are shown in FIG. 8.
Example 4
The graphene composite multilayer porous spherical lithium manganate material prepared in example 1 is used as a positive electrode active material, and the ratio of the positive electrode material to acetylene black and polyvinylidene fluoride is 80:10: mixing at a mass ratio of 10, adopting 1-methyl-2-pyrrolidone as a dispersing agent, uniformly mixing the mixture, mixing into slurry, coating the slurry on an aluminum foil, drying at 60 ℃, cutting to obtain a positive pole piece, adopting a lithium piece as a negative pole (the negative pole capacity is far greater than the capacity of the cut positive pole piece), separating the positive pole piece and the lithium piece by adopting a Celgard 2500 type polypropylene microporous membrane, and adopting 1M LiPF6And the lithium ion battery assembled in the process is subjected to charge and discharge tests at 0.5C rate within a potential range of 3.0V-4.5V at room temperature. The test result shows that the specific discharge capacity of the battery is 137.4mAh/g, and the charge-discharge curve is shown in figure 9.
Example 5
The graphene composite multilayer porous spherical lithium manganate material prepared in example 1 is used as a positive electrode active material, and the ratio of the positive electrode material to acetylene black and sodium carboxymethylcellulose is 80:10: mixing at a mass ratio of 10, adopting water as a dispersing agent, uniformly mixing the mixture to prepare slurry, coating the slurry on an aluminum foil, drying at 60 ℃, cutting to obtain a positive pole piece, adopting a negative pole (the negative pole capacity is far greater than the capacity of the cut positive pole piece), separating the positive pole piece from the lithium piece by adopting a Celgard type polypropylene microporous membrane, and adopting 1M LiPF6Dissolution in EC: and (2) DMC (mass ratio of 1: 1) is used as electrolyte, a stainless steel shell is used as a shell, and the CR2025 type button cell is assembled, wherein the lithium ion battery assembled in the process is subjected to charge and discharge tests at 0.5C multiplying power within a potential range of 3.0V-4.5V at room temperature. The test result shows that the specific discharge capacity of the battery is 132.4 mAh/g, and the charge-discharge curve is shown in figure 10.
Example 6
The graphene composite multilayer porous spherical lithium manganate material prepared in example 1 is used as a positive electrode active material, commercial graphite is used as a negative electrode active material, and the ratio of the positive electrode active material to the negative electrode active material to acetylene black and polyvinylidene fluoride is 80:10: mixing the raw materials according to a mass ratio of 10, adopting 1-methyl-2-pyrrolidone as a dispersing agent, uniformly mixing the mixture, mixing the mixture into slurry, respectively coating the slurry on an aluminum foil and a copper foil, drying and cutting the slurry at 60 ℃ to obtain a corresponding positive pole piece and a corresponding negative pole piece (the negative pole capacity is far greater than the capacity of the cut positive pole piece), separating the pole pieces and the lithium pieces by adopting a Celgard 2500 type polypropylene microporous membrane, and dissolving 1M bis (trifluoromethylsulfonyl) imide lithium in EC: the lithium ion battery assembled in the process is subjected to constant current charge and discharge test at a rate of 1C within a potential range of 2.8V-4.5V at room temperature, a discharge platform is about 3.65V, and a test result shows that the specific discharge capacity of the battery is 113mAh/g, and a charge and discharge curve of the battery is shown in fig. 11.
Example 7
Taking the graphene composite multilayer porous spherical lithium manganate material prepared in example 1 as a positive electrode active material, taking lithium titanate as a negative electrode active material, mixing the positive electrode active material and the negative electrode active material with acetylene black and polyvinylidene fluoride in a ratio of 80:10: mixing the raw materials according to a mass ratio of 10, adopting 1-methyl-2-pyrrolidone as a dispersing agent, uniformly mixing the mixture, mixing the mixture into slurry, respectively coating the slurry on an aluminum foil and a copper foil, drying and cutting the slurry at 60 ℃ to obtain a corresponding positive pole piece and a corresponding negative pole piece (the negative pole capacity is far greater than the capacity of the cut positive pole piece), separating the pole pieces from the lithium pieces by adopting a Celgard 2500 type polypropylene microporous membrane, and dissolving 1M lithium trifluoromethanesulfonate in EC: the lithium ion battery assembled in the process is subjected to constant current charge and discharge test at a potential range of 1.5V-3.0V and a constant current multiplying power of 0.5C at room temperature, a discharge platform is mainly 2.4-2.7V, and test results show that the specific discharge capacity of the battery is 104mAh/g, and the charge and discharge curve of the battery is shown in figure 12.
Example 8
The particle size of the spherical lithium manganate electrode material in the embodiment is 1 μm.
The amount of graphene in the lithium manganate electrode material is 10% of the mass of the spherical lithium manganate.
The preparation method of the lithium manganate electrode material comprises the following steps:
(1) dissolving 0.25g of hexadecyl trimethyl ammonium bromide and 11.25g of ammonium bicarbonate in 250ml of deionized water to form a first mixed solution;
(2) dissolving 2.54g of manganese sulfate in 241.3g of deionized water to form a mixed solution II;
(3) placing the mixed solution I obtained in the step (1) in an oil bath at 50 ℃, dropwise adding the mixed solution II obtained in the step (2) into the mixed solution I for 30min, adjusting the pH to 7.5 after the dropwise adding is finished, and keeping the mixed solution in the oil bath for 30min to obtain a turbid solution;
(4) standing the turbid solution obtained in the step (3) for 24 hours, washing with water, centrifuging, and drying at 60-80 ℃ to obtain manganese carbonate primary powder, wherein the manganese carbonate primary powder is calcined at 730 ℃ to obtain a precursor manganese sesquioxide;
(5) adding 0.35g of the precursor manganese sesquioxide obtained in the step (4) and 0.1g of lithium perchlorate into 1ml of absolute ethyl alcohol for grinding, placing the ground mixture into a tubular furnace in an oxygen atmosphere for presintering at 560 ℃ for 4h, and heating to 750 ℃ for calcining for 10h to obtain multilayer porous spherical lithium manganate;
(6) and (3) dispersing graphene in deionized water, performing ultrasonic treatment for 1 h, adding the multilayer porous spherical lithium manganate obtained in the step (5), stirring for 4h, and performing centrifugal drying to obtain the lithium manganate electrode material.
The lithium manganate electrode material prepared in the embodiment is used as a positive electrode material, a carbon material capable of intercalating and deintercalating lithium ions is used as a negative electrode material, the positive electrode material is mixed with carbon black and sodium carboxymethylcellulose in a mass ratio of 80:10:10, and ethanol is used as a dispersing agent; and uniformly mixing the mixture to form slurry, coating the slurry on carbon cloth, drying at 60 ℃, and cutting to obtain the positive pole piece. And separating the positive pole piece from the lithium piece by a Polyethylene (PE) microporous membrane.
Lithium perchlorate is dissolved in dimethyl carbonate and diethyl carbonate (1: 1) to prepare electrolyte, and organic plastic is used as a shell to prepare the lithium ion battery.
Example 9
The particle size of the spherical lithium manganate electrode material in the embodiment is 2 μm.
The amount of graphene in the lithium manganate electrode material is 20% of the mass of the spherical lithium manganate.
The preparation method of the lithium manganate electrode material comprises the following steps:
(1) dissolving 0.25g of hexadecyl trimethyl ammonium bromide and 10g of ammonium bicarbonate in 250ml of deionized water to form a first mixed solution;
(2) 2.54g of manganese sulfate is dissolved in 228.6g of deionized water to form a mixed solution II;
(3) placing the mixed solution I obtained in the step (1) in an oil bath at 50 ℃, dropwise adding the mixed solution II obtained in the step (2) into the mixed solution I for 30min, adjusting the pH to 7 after the dropwise adding is finished, and keeping the mixed solution in the oil bath for 30min to obtain a turbid solution;
(4) standing the turbid solution obtained in the step (3) for 24 hours, washing with water, centrifuging, drying at 60-80 ℃ to obtain manganese carbonate primary powder, and calcining the manganese carbonate primary powder at 800 ℃ to obtain a precursor manganese sesquioxide;
(5) adding 0.4g of the precursor manganese sesquioxide obtained in the step (4) and 0.1g of lithium tetrafluoroborate into 1ml of absolute ethyl alcohol for grinding, placing the ground mixture into a tubular furnace in an oxygen atmosphere for presintering at 500 ℃ for 6h, and heating to 800 ℃ for calcining for 8h to obtain multilayer porous spherical lithium manganate;
(6) and (3) dissolving the graphene slurry in deionized water, performing ultrasonic treatment for 1 h, adding the multilayer porous spherical lithium manganate obtained in the step (5), stirring for 4h, and performing centrifugal drying to obtain the lithium manganate electrode material.
The lithium manganate electrode material prepared by the embodiment is used as a positive electrode material, a titanium-based material capable of intercalating and deintercalating lithium ions is used as a negative electrode material, the positive electrode material is mixed with graphite and polyvinylidene fluoride according to a mass ratio of 80:10:10, and isopropanol is used as a dispersing agent; and uniformly mixing the mixture to form slurry, coating the slurry on an aluminum porous material, drying at 60 ℃, and cutting to obtain the positive pole piece. And separating the positive pole piece from the lithium piece by adopting a polyimide film (PI) diaphragm.
Lithium tetrafluoroborate is dissolved in dimethyl carbonate, diethyl carbonate and tetrahydrofuran to prepare electrolyte, and an aluminum shell is taken as a shell to prepare the lithium ion battery.
Example 10
The particle size of the spherical lithium manganate electrode material in the embodiment is 5 μm.
The amount of graphene in the lithium manganate electrode material is 1% of the mass of the spherical lithium manganate.
The preparation method of the lithium manganate electrode material comprises the following steps:
(1) dissolving 0.25g of hexadecyl trimethyl ammonium bromide and 10g of ammonium bicarbonate in 250ml of deionized water to form a first mixed solution;
(2) 2.54g of manganese sulfate is dissolved in 228.6g of deionized water to form a mixed solution II;
(3) placing the mixed solution I obtained in the step (1) in an oil bath at 50 ℃, dropwise adding the mixed solution II obtained in the step (2) into the mixed solution I for 30min, adjusting the pH to 8 after the dropwise adding is finished, and keeping the mixed solution in the oil bath for 30min to obtain a turbid solution;
(4) standing the turbid solution obtained in the step (3) for 24 hours, washing with water, centrifuging, and drying at 60-80 ℃ to obtain manganese carbonate primary powder, wherein the manganese carbonate primary powder is calcined at 600 ℃ to obtain a precursor manganese sesquioxide;
(5) adding 0.3g of the precursor manganese sesquioxide obtained in the step (4) and 0.1g of lithium hexafluoroarsenate into 1ml of absolute ethyl alcohol for grinding, placing the ground mixture into a tubular furnace in an oxygen atmosphere for presintering at 600 ℃ for 2h, and heating to 600 ℃ for calcining for 15h to obtain multilayer porous spherical lithium manganate;
(6) and (3) dispersing graphene in deionized water, performing ultrasonic treatment for 1 h, adding the multilayer porous spherical lithium manganate obtained in the step (5), stirring for 4h, and performing centrifugal drying to obtain the lithium manganate electrode material.
The lithium manganate electrode material prepared in the embodiment is used as a positive electrode material, a composite material of a carbon material capable of intercalating and deintercalating lithium ions and a titanium-based material is used as a negative electrode material, the positive electrode material, carbon black and polytetrafluoroethylene are mixed according to a mass ratio of 80:10:10, and isopropanol is used as a dispersing agent; and uniformly mixing the mixture to form slurry, coating the slurry on an aluminum mesh material, drying at 60 ℃, and cutting to obtain the positive pole piece. The positive pole piece and the lithium piece are separated by a polypropylene (PP) microporous membrane.
Lithium perchlorate is dissolved in ethylene carbonate and tetrahydrofuran (1: 1) to prepare electrolyte, and an aluminum shell is taken as a shell to prepare the lithium ion battery.
Example 11
The preparation method of the spherical lithium manganate electrode material in the embodiment is the same as that in embodiment 1.
The lithium manganate electrode material prepared in the embodiment is used as a positive electrode material, a lithium sheet is used as a negative electrode material, the positive electrode material is mixed with acetylene black and polyacrylic acid in a mass ratio of 80:10:10, and an isopropanol dispersant is adopted; and uniformly mixing the mixture to form slurry, coating the slurry on a nickel film material, drying at 60 ℃, and cutting to obtain the positive pole piece. The positive pole piece and the lithium piece are separated by a polypropylene (PP) microporous membrane.
Dissolving lithium bis (trifluoromethylsulfonyl) imide in diethyl carbonate, dimethyl ether and tetrahydrofuran (the volume ratio of the diethyl carbonate, the dimethyl ether and the tetrahydrofuran is 1:1: 1) to prepare an electrolyte, and taking organic plastic as a shell to prepare the lithium ion battery.
Example 12
The preparation method of the spherical lithium manganate electrode material in the embodiment is the same as that in embodiment 1.
The lithium manganate electrode material prepared in the embodiment is used as a positive electrode material, a lithium sheet is used as a negative electrode material, the positive electrode material is mixed with graphite and polytetrafluoroethylene in a mass ratio of 80:10:10, and 1-methyl-2-pyrrolidone is used as a dispersing agent; and uniformly mixing the mixture to prepare slurry, coating the slurry on a metal stainless steel material, drying at 60 ℃, and cutting to obtain the positive pole piece. And separating the positive pole piece from the lithium piece by adopting a glass fiber diaphragm.
Dissolving lithium trifluoromethanesulfonate in diethyl carbonate, dimethyl ether and tetrahydrofuran to prepare electrolyte, and using stainless steel and its composite material as casing to prepare the lithium ion battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The utility model provides a compound multilayer of graphite alkene foraminiferous spherical lithium manganate electrode material which characterized in that: the graphene composite multilayer porous spherical lithium manganate electrode material is formed by uniformly dispersing graphene with a lamellar structure around lithium manganate particles, wherein the lithium manganate is an open and multilayer porous spherical structure formed by stacking primary particles, the particle size of the primary particles is 100-200 nm, and the particle size of the stacked multilayer porous spherical lithium manganate electrode material is 1-5 mu m;
the preparation method of the graphene composite multilayer porous spherical lithium manganate electrode material comprises the following steps:
(1) dissolving cetyl trimethyl ammonium bromide and ammonium bicarbonate in deionized water to form a mixed solution I; the mass ratio of the hexadecyl trimethyl ammonium bromide to the ammonium bicarbonate to the deionized water is 1: (40-50): 1000, parts by weight;
(2) dissolving manganese sulfate in deionized water to form a mixed solution II; the mass ratio of manganese sulfate to deionized water is 1: (80-100);
(3) placing the mixed solution I obtained in the step (1) in an oil bath at the temperature of 40-60 ℃, dropwise adding the mixed solution II obtained in the step (2) into the mixed solution I, and adjusting the pH value to 7.5 after the dropwise adding is finished to obtain a turbid solution;
(4) washing the turbid solution obtained in the step (3) with water, centrifuging, and drying to obtain manganese carbonate primary powder, wherein the manganese carbonate primary powder is calcined at the temperature of 600-800 ℃ to obtain a precursor manganese sesquioxide;
(5) adding the precursor manganous oxide and lithium salt obtained in the step (4) into absolute ethyl alcohol for grinding, wherein the molar ratio of the precursor manganous oxide to the lithium salt is (8-10): 1, uniformly grinding, placing in a tubular furnace in an oxygen atmosphere, presintering at the temperature of 500-600 ℃ for 2-6h, heating to the temperature of 600-800 ℃ and calcining for 8-15 h to obtain multilayer porous spherical lithium manganate;
(6) and (3) dispersing graphene in deionized water, adding the multilayer porous spherical lithium manganate obtained in the step (5), stirring, centrifuging and drying to obtain the graphene composite multilayer porous spherical lithium manganate electrode material.
2. The graphene composite multilayer spherical lithium manganate electrode material as claimed in claim 1, wherein: the mass of graphene in the graphene composite multilayer spherical lithium manganate electrode material is 1% -20% of the mass of lithium manganate.
3. The utility model provides a lithium ion battery, mainly comprises positive plate, negative pole piece, electrolyte, diaphragm and shell, its characterized in that: the lithium ion battery adopts the graphene composite multilayer porous spherical lithium manganate electrode material as defined in claim 1 as a positive electrode material, adopts metal lithium or an intercalation/deintercalation lithium active material as a negative electrode material, adopts a polyethylene or polypropylene microporous membrane or a glass fiber membrane as a membrane, and adopts a soluble lithium salt organic solution as an electrolyte.
4. The lithium ion battery of claim 3, wherein: the positive plate and the negative plate are respectively obtained by filling slurry obtained by uniformly mixing a positive material and a negative material with a conductive agent, a binder and a dispersing agent into a current collector, wherein the current collector is made of carbon cloth, metal stainless steel, porous nickel, porous aluminum or a film material.
5. The lithium ion battery of claim 3, wherein: the lithium-ion-intercalation/deintercalation active material is a carbon material or a titanium-based material which can intercalate/deintercalate lithium ions, or is a composite material of the carbon material and the titanium-based material which can intercalate/deintercalate lithium ions.
6. The lithium ion battery of claim 4, wherein: the conductive agent is carbon black or graphite; the binder is polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, polyacrylic acid or styrene butadiene rubber; the dispersant is water, ethanol, isopropanol or 1-methyl-2-pyrrolidone.
7. The lithium ion battery of claim 3, wherein: the soluble lithium salt organic solution is obtained by dissolving lithium salt in an organic solvent, wherein the lithium salt is one or more of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate and lithium bis (trifluoromethanesulfonyl) imide, and the organic solvent is one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dimethyl ether and tetrahydrofuran.
8. The lithium ion battery of claim 3, wherein: the shell is made of organic plastics, an aluminum shell, an aluminum plastic film or stainless steel and is in a buckled, columnar or square shape.
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| CN108448092A (en) * | 2018-03-20 | 2018-08-24 | 桂林理工大学 | A kind of preparation method with high rate capability and cycle performance LiMn2O4/three-dimensional graphene composite material |
| CN108847481B (en) * | 2018-06-29 | 2020-11-24 | 华南师范大学 | Preparation and application of carbon-coated porous manganous oxide cubic cathode material for high-performance lithium ion battery |
| CN110190277B (en) * | 2019-06-06 | 2022-05-03 | 电子科技大学 | Lithium ion battery anode material LiMnO2@ C and preparation method thereof |
| CN110176595B (en) * | 2019-06-06 | 2022-06-03 | 电子科技大学 | Lithium ion battery anode material LiMnO2@ C and preparation method thereof |
| CN111239222B (en) * | 2020-01-16 | 2022-12-02 | 郑州大学 | Ionic liquid electrolyte and electrochemical gas sensor |
| CN111916748A (en) * | 2020-08-14 | 2020-11-10 | 张超 | Spherical nano graphene conductive paste |
| CN114094061A (en) * | 2021-10-09 | 2022-02-25 | 温州大学 | Rice-grain-shaped manganese carbonate composite graphene high-performance lithium storage material and lithium battery |
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