CN114284483A - Preparation and application of a zirconium dioxide-coated lithium manganate cathode material - Google Patents
Preparation and application of a zirconium dioxide-coated lithium manganate cathode material Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 43
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010406 cathode material Substances 0.000 title claims description 15
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000007774 positive electrode material Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000010405 anode material Substances 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 9
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 6
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000853 adhesive Substances 0.000 claims abstract description 4
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- 238000004537 pulping Methods 0.000 claims abstract description 4
- 239000011343 solid material Substances 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 28
- 239000011888 foil Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 24
- 238000012360 testing method Methods 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000006230 acetylene black Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 230000007246 mechanism Effects 0.000 claims description 3
- 239000011268 mixed slurry Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000007767 bonding agent Substances 0.000 abstract 1
- 238000004080 punching Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- -1 Al (OH)3 Chemical compound 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001652 electrophoretic deposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
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Abstract
The invention relates to the technical field of electrochemistry, in particular to a preparation method and application of a zirconium dioxide coated lithium manganate positive electrode material, which comprises the following steps: s1, weighing materials: weighing manganese dioxide (MnO 2), lithium fluoride (LiF), aluminum hydroxide (Al (OH) 3), zirconium dioxide (ZrO ₂), lithium carbonate (Li 2CO 3), a dispersing agent and a bonding agent according to a stoichiometric ratio; s2, grinding and pulping: and pouring the solid materials into a ball mill in sequence, starting the ball mill to grind the materials, and pouring the dispersing agent and the adhesive into the ball mill to mix and grind during grinding so as to prepare uniform slurry. The method has the beneficial effects that when the zirconium dioxide coating method is used for producing the lithium manganate anode material, the generated LMO-Al-F-3% material can improve the high-temperature cycle performance of the lithium manganate battery, so that the electrochemical performance of the lithium manganate battery is improved.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to preparation and application of a zirconium dioxide coated lithium manganate positive electrode material.
Background
Lithium ions are receiving the attention of scientists because of their advantages of high energy density, long cycle life, low self-discharge capability, no memory effect, etc. In recent years, the battery is widely used in portable electronic devices and is shifted to the fields of electric vehicles and large-scale energy storage, and the safety and manufacturing cost of the battery are important concerns in these fields. Lithium manganate is one of the most widely used positive electrode materials due to the characteristics of abundant reserves, low material cost, high safety and the like.
Chinese patent No. CN105742610B provides a preparation method of a carbon-coated lithium ferric manganese phosphate film type anode material, which comprises the steps of firstly grinding, polishing, cleaning and drying a ferro-manganese alloy material; taking a substrate material as an anode and a stainless steel sheet as a cathode, simultaneously immersing the substrate material and the stainless steel sheet into micro-arc oxidation electrolyte for micro-arc oxidation treatment, and uniformly covering a layer of ferric manganese phosphate with a microporous structure on the surface of the substrate material; adding a lithium source into absolute ethyl alcohol, taking graphite as an anode and taking a matrix material coated with iron and manganese phosphate as a cathode, and carrying out electrophoretic deposition under the condition that the voltage is 20-60V, wherein lithium is deposited on the iron and manganese phosphate to obtain a lithium manganese iron phosphate precursor; and depositing carbon on the lithium manganese iron phosphate precursor by a carbon source through a chemical vapor deposition method to obtain the carbon-coated lithium manganese iron phosphate film-type cathode material.
At present, the technical process of the lithium manganate coating modification of the above scheme is relatively complex, so that the production cost of the lithium battery is too high, meanwhile, the structural stability of the existing lithium manganate positive electrode material produced by the prior art is not good, and the high-temperature cycle performance of the lithium ion battery assembled by the lithium manganate positive electrode material is poor, so that the preparation and application of the lithium manganate positive electrode material coated by zirconium dioxide are urgently needed to be designed to solve the above problems.
Disclosure of Invention
The invention aims to provide a method for improving the stability of a lithium manganate anode material, and the method is used for solving the problems that the existing lithium manganate coating modification process is complex, the lithium manganate anode material is poor in structural stability, and the high-temperature cycle performance of a battery is poor in the background art.
The technical scheme of the invention is as follows: the preparation method of the zirconium dioxide coated lithium manganate cathode material comprises the following steps:
s1, weighing materials: weighing manganese dioxide (MnO 2), lithium fluoride (LiF), aluminum hydroxide (Al (OH) 3) and zirconium dioxide (ZrO) according to stoichiometric ratio2) Lithium carbonate (Li 2CO 3), a dispersant, a binder;
s2, grinding and pulping: pouring the solid materials into a ball mill in sequence, then starting the ball mill to grind the materials, and pouring the dispersing agent and the adhesive into the ball mill to mix and grind during grinding, thereby preparing uniform slurry;
s3, spray granulation: pouring the slurry prepared in the step into a spray dryer, and then starting the spray dryer to carry out atomization drying on the slurry so as to obtain proper mixture particles;
s4, high-temperature sintering: after the previous step is finished, putting the obtained particles into a sagger, pushing the sagger into a sintering furnace, and then starting the sintering furnace to roast the mixture in the sagger;
s5, cooling and crushing: after the sintering in the previous step is finished, the sagger can be placed in air cooling equipment, the LiMn1.95Al0.05O3.8F0.2@ xZrO2 positive electrode material with regular appearance and uniform particle size distribution is obtained after the sagger is cooled to the room temperature, then the hardened mixture can be taken out and put into a crusher, so that the mixture is crushed, and then the mixture is poured into grinding equipment for grinding, so that the lithium manganate positive electrode material is obtained.
Further, the lithium carbonate in S1 is lithium carbonate with an excess of 3%, the dispersant is one of pure water and ethanol, and the binder is polyethylene glycol (PEG).
Further, the ball mill in the S2 is a planetary ball mill, and the milling time is 4-8 h.
Further, the solid-liquid ratio is controlled to be 1: 1-1.5 during spray granulation in S3, the air outlet temperature is 90-150 ℃, the feeding speed is 15-30mL/min, the temperature after dust collection is 120 ℃, and the time is 10-15 hours.
Further, in the step S4, pre-sintering is performed at a high temperature for 1-3 hours at a temperature of 450-.
The application of the zirconium dioxide coated lithium manganate cathode material comprises the following steps:
s1, stirring and mixing: the prepared positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) are poured into mixing equipment together, then a proper amount of solvent N-methyl pyrrolidone solution is added, then the mixing equipment is started, so that the materials are mixed, and then mixture slurry is obtained;
s2, coating: pouring the mixed slurry into a slurry storage mechanism of coating equipment, and then starting the coating equipment to uniformly coat the slurry on the aluminum foil;
s3, vacuum drying: putting the coated aluminum foil into vacuum drying equipment, starting the drying equipment to dry the aluminum foil, and then placing the aluminum foil in a room temperature environment for cooling;
s4, tabletting and stamping: when the dried aluminum foil is cooled to room temperature, placing the aluminum foil on a tablet press, and then starting the tablet press to punch the aluminum foil, so as to obtain a composite electrode wafer;
s5, assembling: the obtained wafer is used as a positive electrode, a metal lithium sheet is used as a negative electrode, Celgard-2400 is used as a diaphragm, a 1mol/LLiPF6(EC + DMC) (volume ratio is 1: 1) mixed solution is used as an electrolyte, and then the materials are assembled into a CR 2025 type button cell in a glove box filled with argon;
s6, product testing: after the button cell is manufactured in the previous step, the button cell can be placed in a LANDCT2001A type cell testing system, and then the system is started to perform charging and discharging tests on the button cell.
Further, the proportion of the anode material, the acetylene black and the PVDF in the S1 is 8: 1, the stirring speed is 300-500r/min during the mixing by the mixing device in the S1, and the time is 15-30 min.
Further, the thickness of the aluminum foil selected by the S2 is 15-25 μm, and the coating thickness is 5-10 μm.
Further, the vacuum drying time in the S3 is 5-8h, and the temperature is 100-150 ℃.
Furthermore, the composite electrode wafer punched by the pressing sheet in the S4 is 10-15 mm.
The invention provides a preparation method and application of a zirconium dioxide coated lithium manganate positive electrode material through improvement, compared with the prior art, the preparation method has the following improvement and advantages:
(1) according to the zirconium dioxide coating method designed by the invention, when the method is used for producing the lithium manganate cathode material, the generated LMO-Al-F-3% material can improve the high-temperature cycle performance of the lithium manganate battery, so that the electrochemical performance of the lithium manganate battery is improved.
(2) According to the spray drying method designed by the invention, when the method is used for preparing the lithium manganate cathode material, the spray drying method can successfully prepare the spherical precursor with regular appearance and uniform particle size distribution, so that the structural stability of the cathode material is improved.
(3) According to the process method designed by the invention, the F, Al co-doped spinel lithium manganate material coated on the surface of the ZrO2 synthesized in one step has the characteristics of simple process, environmental friendliness and the like, and the future development space of the lithium manganate battery can be improved.
Drawings
The invention is further explained below with reference to the figures and examples:
FIG. 1 is a flow chart of a method of the present invention;
fig. 2 is a flow chart of an application of the present invention.
Detailed Description
The present invention will be described in detail with reference to fig. 1-2, and the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
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 to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a preparation method of a zirconium dioxide coated lithium manganate cathode material by improvement, as shown in figure 1, comprising the following steps:
s1, weighing materials: weighing manganese dioxide (MnO 2), lithium fluoride (LiF), aluminum hydroxide (Al (OH) 3) and zirconium dioxide (ZrO) according to stoichiometric ratio2) 3% excess of lithium carbonate (Li 2CO 3), water, polyethylene glycol;
s2, grinding and pulping: pouring the solid materials into a planetary ball mill in sequence, then starting the ball mill to grind the materials, pouring a dispersing agent and an adhesive into the ball mill to mix and grind during grinding, wherein the grinding time is 6 hours, so as to prepare uniform slurry;
s3, spray granulation: pouring the slurry prepared in the steps into a spray dryer, starting a spray drying agent to carry out spray drying on the slurry, controlling the solid-liquid ratio to be 1: 1-1.5 during spray granulation, controlling the air outlet temperature to be 120 ℃, the feeding speed to be 20mL/min, controlling the temperature to be 120 ℃ after dust collection, and controlling the time to be 12 hours, thereby obtaining proper mixture particles;
s4, high-temperature sintering: after the previous step is finished, putting the obtained particles into a sagger, pushing the sagger into a sintering furnace, and then starting the sintering furnace to roast the mixture in the sagger, wherein the precalcination is carried out at high temperature for 3 hours at 500 ℃, the temperature is 750 ℃ during the high-temperature roasting, and the time is 24 hours;
s5, cooling and crushing: after the sintering in the previous step is finished, the sagger can be placed in air cooling equipment, the LiMn1.95Al0.05O3.8F0.2@ xZrO2 positive electrode material with regular appearance and uniform particle size distribution is obtained after the sagger is cooled to the room temperature, then the hardened mixture can be taken out and put into a crusher, so that the mixture is crushed, and then the mixture is poured into grinding equipment for grinding, so that the lithium manganate positive electrode material is obtained.
An application of a zirconium dioxide-coated lithium manganate positive electrode material is shown in fig. 2, and comprises the following steps:
s1, stirring and mixing: the prepared positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) are poured into mixing equipment together according to the ratio of 8: 1, then a proper amount of solvent N-methyl pyrrolidone solution is added, then the mixing equipment is started, so that the materials are mixed, the stirring speed is 500r/min, the time is 20min, and then mixture slurry is obtained;
s2, coating: pouring the mixed slurry into a slurry storage mechanism of coating equipment, and then starting the coating equipment to uniformly coat the slurry on an aluminum foil with the thickness of 20 microns, wherein the coating thickness is 8 microns;
s3, vacuum drying: putting the coated aluminum foil into vacuum drying equipment, starting the drying equipment to dry the aluminum foil, wherein the vacuum drying time is 6 hours, the temperature is 120 ℃, and then placing the aluminum foil in a room temperature environment for cooling;
s4, tabletting and stamping: when the dried aluminum foil is cooled to room temperature, placing the aluminum foil on a tablet press, and then starting the tablet press to punch the aluminum foil, so as to obtain a composite electrode wafer with the thickness of 12 mm;
s5, assembling: the obtained wafer is used as a positive electrode, a metal lithium sheet is used as a negative electrode, Celgard-2400 is used as a diaphragm, a 1mol/LLiPF6(EC + DMC) (volume ratio is 1: 1) mixed solution is used as an electrolyte, and then the materials are assembled into a CR 2025 type button cell in a glove box filled with argon;
s6, product testing: after the button cell is manufactured in the previous step, the button cell can be placed in a LANDCT2001A type cell testing system, and then the system is started to perform charging and discharging tests on the button cell.
Example one
The application of the zirconium dioxide coated lithium manganate cathode material comprises the following steps:
selecting a LiMn1.95Al0.05O3.8F0.2@ xZrO2 material with the ZrO2 coating amount of 1%, mixing the anode material, acetylene black and PVDF according to the mass ratio of 8: 1, and adding a proper amount of solvent N-methylpyrrolidone solution for size mixing. It was uniformly coated on a 20 μm thick aluminum foil and then vacuum-dried at 120 ℃ for 6 hours. And punching into a composite electrode circular sheet with the diameter of 12.0mm by using a tablet machine. The obtained wafer was used as a positive electrode, a metal lithium plate was used as a negative electrode, Celgard-2400 was used as a separator, a 1mol/LLIPF6(EC + DMC) (volume ratio 1: 1) mixed solution was used as an electrolyte, a CR 2025 button cell was assembled in an argon-filled glove box, and then a charge/discharge test was performed using a LANDCT2001A battery test system.
Example two
The application of the zirconium dioxide coated lithium manganate cathode material comprises the following steps:
selecting a LiMn1.95Al0.05O3.8F0.2@ xZrO2 material with the ZrO2 coating amount of 3%, mixing the anode material, acetylene black and PVDF according to the mass ratio of 8: 1, and adding a proper amount of solvent N-methylpyrrolidone solution for size mixing. It was uniformly coated on a 20 μm thick aluminum foil and then vacuum-dried at 120 ℃ for 6 hours. And punching into a composite electrode circular sheet with the diameter of 12.0mm by using a tablet machine. The obtained wafer was used as a positive electrode, a metal lithium plate was used as a negative electrode, Celgard-2400 was used as a separator, a 1mol/LLIPF6(EC + DMC) (volume ratio 1: 1) mixed solution was used as an electrolyte, a CR 2025 button cell was assembled in an argon-filled glove box, and then a charge/discharge test was performed using a LANDCT2001A battery test system.
EXAMPLE III
The application of the zirconium dioxide coated lithium manganate cathode material comprises the following steps:
selecting a LiMn1.95Al0.05O3.8F0.2@ xZrO2 material with the ZrO2 coating amount of 5%, mixing the anode material, acetylene black and PVDF according to the mass ratio of 8: 1, and adding a proper amount of solvent N-methylpyrrolidone solution for size mixing. It was uniformly coated on a 20 μm thick aluminum foil and then vacuum-dried at 120 ℃ for 6 hours. And punching into a composite electrode circular sheet with the diameter of 12.0mm by using a tablet machine. The obtained wafer was used as a positive electrode, a metal lithium plate was used as a negative electrode, Celgard-2400 was used as a separator, a 1mol/LLIPF6(EC + DMC) (volume ratio 1: 1) mixed solution was used as an electrolyte, a CR 2025 button cell was assembled in an argon-filled glove box, and then a charge/discharge test was performed using a LANDCT2001A battery test system.
Example four
The application of the zirconium dioxide coated lithium manganate cathode material comprises the following steps:
selecting a LiMn1.95Al0.05O3.8F0.2 material with the ZrO2 coating amount of 0%, mixing the anode material, acetylene black and PVDF according to the mass ratio of 8: 1, and adding a proper amount of solvent N-methylpyrrolidone solution for size mixing. It was uniformly coated on a 20 μm thick aluminum foil and then vacuum-dried at 120 ℃ for 6 hours. And punching into a composite electrode circular sheet with the diameter of 12.0mm by using a tablet machine. The obtained wafer was used as a positive electrode, a metal lithium plate was used as a negative electrode, Celgard-2400 was used as a separator, a 1mol/LLIPF6(EC + DMC) (volume ratio 1: 1) mixed solution was used as an electrolyte, a CR 2025 button cell was assembled in an argon-filled glove box, and then a charge/discharge test was performed using a LANDCT2001A battery test system.
The wrapping amounts of ZrO2 adopted in the first embodiment, the second embodiment, the third embodiment and the fourth embodiment are different, and the other parameters are consistent, and the charge-discharge experimental comparison is performed on the button cell finally obtained, so that the detection data are as follows:
| experimental number | Specific discharge capacity retention rate after 260 cycles of circulation under 1C condition | Specific discharge capacity (mAh/g) at 0.1C rate |
| Example 1 | 74.5% | 124 |
| Example 2 | 82.4% | 120 |
| Example 3 | 63.2% | 118 |
| Example 4 | 65.1% | 112 |
Thus, the second embodiment has the best effect.
The working principle is as follows: preparing materials: weighing electrolytic MnO2, LiF, Al (OH)3, ZrO2 and Li2CO3 with the excess of 3% according to the stoichiometric ratio, taking H2O as a dispersing agent and PEG as a binder, and mixing and ball-milling for 6 hours in a planetary ball mill to prepare uniform slurry. Granulating by a spray dryer, controlling the solid-liquid ratio to be 1: 1-1.5, controlling the air outlet temperature to be 90-150 ℃, the feeding speed to be 15-30mL/min, drying at 120 ℃ for @12h after dust collection, presintering at 500 ℃ for 3h and high-temperature roasting at 750 ℃ for 24h in the air atmosphere, and cooling to room temperature to obtain the LiMn1.95Al0.05O3.8F0.2@ xZrO2 material with regular appearance and uniform particle size distribution
Preparing a battery: mixing the anode material, acetylene black and PVDF according to the mass ratio of 8: 1, and adding a proper amount of solvent N-methyl pyrrolidone solution for size mixing. It was uniformly coated on a 20 μm thick aluminum foil and then vacuum-dried at 120 ℃ for 6 hours. And punching into a composite electrode circular sheet with the diameter of 12.0mm by using a tablet machine. The obtained wafer is used as a positive electrode, a metal lithium sheet is used as a negative electrode, Celgard-2400 is used as a diaphragm, a mixed solution of 1mol/LLiPF6(EC + DMC) (the volume ratio is 1: 1) is used as an electrolyte, and a CR 2025 button cell is assembled in a glove box filled with argon. The charge and discharge test was performed using a model LANDCT2001A battery test system.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the zirconium dioxide-coated lithium manganate cathode material is characterized by comprising the following steps: the method comprises the following steps:
s1, weighing materials: weighing manganese dioxide (MnO 2), lithium fluoride (LiF), aluminum hydroxide (Al (OH) 3) and zirconium dioxide (ZrO) according to stoichiometric ratio2) Lithium carbonate (Li 2CO 3), a dispersant, a binder;
s2, grinding and pulping: pouring the solid materials into a ball mill in sequence, then starting the ball mill to grind the materials, and pouring the dispersing agent and the adhesive into the ball mill to mix and grind during grinding, thereby preparing uniform slurry;
s3, spray granulation: pouring the slurry prepared in the step into a spray dryer, and then starting the spray dryer to carry out atomization drying on the slurry so as to obtain proper mixture particles;
s4, high-temperature sintering: after the previous step is finished, putting the obtained particles into a sagger, pushing the sagger into a sintering furnace, and then starting the sintering furnace to roast the mixture in the sagger;
s5, cooling and crushing: after the sintering in the previous step is finished, the sagger can be placed in air cooling equipment, the LiMn1.95Al0.05O3.8F0.2@ xZrO2 positive electrode material with regular appearance and uniform particle size distribution is obtained after the sagger is cooled to the room temperature, then the hardened mixture can be taken out and put into a crusher, so that the mixture is crushed, and then the mixture is poured into grinding equipment for grinding, so that the lithium manganate positive electrode material is obtained.
2. The preparation method of the zirconium dioxide-coated lithium manganate positive electrode material according to claim 1, wherein the preparation method comprises the following steps: the lithium carbonate in the S1 is lithium carbonate with an excess of 3%, the dispersant is one of pure water and ethanol, and the binder is polyethylene glycol (PEG).
3. The preparation method of the zirconium dioxide-coated lithium manganate positive electrode material according to claim 1, wherein the preparation method comprises the following steps: the ball mill in the S2 is a planetary ball mill, and the milling time is 4-8 h.
4. The preparation method of the zirconium dioxide-coated lithium manganate positive electrode material according to claim 1, wherein the preparation method comprises the following steps: and in the S3, the solid-liquid ratio is controlled to be 1: 1-1.5 during spray granulation, the air outlet temperature is 90-150 ℃, the feeding speed is 15-30mL/min, the temperature is 120 ℃ after dust collection, and the time is 10-15 h.
5. The preparation method of the zirconium dioxide-coated lithium manganate positive electrode material according to claim 1, wherein the preparation method comprises the following steps: the step S4 is to pre-bake at high temperature for 1-3h at 450-600 deg.C for 18-30h at 700-800 deg.C.
6. The application of the zirconium dioxide coated lithium manganate cathode material is characterized in that: the method comprises the following steps:
s1, stirring and mixing: the prepared positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) are poured into mixing equipment together, then a proper amount of solvent N-methyl pyrrolidone solution is added, then the mixing equipment is started, so that the materials are mixed, and then mixture slurry is obtained;
s2, coating: pouring the mixed slurry into a slurry storage mechanism of coating equipment, and then starting the coating equipment to uniformly coat the slurry on the aluminum foil;
s3, vacuum drying: putting the coated aluminum foil into vacuum drying equipment, starting the drying equipment to dry the aluminum foil, and then placing the aluminum foil in a room temperature environment for cooling;
s4, tabletting and stamping: when the dried aluminum foil is cooled to room temperature, placing the aluminum foil on a tablet press, and then starting the tablet press to punch the aluminum foil, so as to obtain a composite electrode wafer;
s5, assembling: the obtained wafer is used as a positive electrode, a metal lithium sheet is used as a negative electrode, Celgard-2400 is used as a diaphragm, a 1mol/LLiPF6(EC + DMC) (volume ratio is 1: 1) mixed solution is used as an electrolyte, and then the materials are assembled into a CR 2025 type button cell in a glove box filled with argon;
s6, product testing: after the button cell is manufactured in the previous step, the button cell can be placed in a LANDCT2001A type cell testing system, and then the system is started to perform charging and discharging tests on the button cell.
7. The application of the zirconium dioxide-coated lithium manganate positive electrode material as claimed in claim 6, wherein: the proportion of the anode material, the acetylene black and the PVDF in the S1 is 8: 1, the stirring speed is 300-500r/min during the mixing by the mixing device in the S1, and the time is 15-30 min.
8. The application of the zirconium dioxide-coated lithium manganate positive electrode material as claimed in claim 6, wherein: the thickness of the aluminum foil selected by the S2 is 15-25 μm, and the coating thickness is 5-10 μm.
9. The application of the zirconium dioxide-coated lithium manganate positive electrode material as claimed in claim 6, wherein: the vacuum drying time in the S3 is 5-8h, and the temperature is 100-150 ℃.
10. The application of the zirconium dioxide-coated lithium manganate positive electrode material as claimed in claim 6, wherein: and the composite electrode wafer punched by the pressing sheet in the S4 is 10-15 mm.
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