CN109004212B - High-rate lithium manganate positive electrode material and preparation method thereof - Google Patents
High-rate lithium manganate positive electrode material and preparation method thereof Download PDFInfo
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- 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 92
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011029 spinel Substances 0.000 claims abstract description 44
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 42
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000001694 spray drying Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011572 manganese Substances 0.000 claims abstract description 9
- 239000010406 cathode material Substances 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 4
- 238000000498 ball milling Methods 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 23
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 10
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000004005 microsphere Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011164 primary particle Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 229910007913 Li-Al-Ti-P-O Inorganic materials 0.000 claims description 2
- 229910015645 LiMn Inorganic materials 0.000 claims description 2
- 229910008474 Li—Al—Ti—P—O Inorganic materials 0.000 claims description 2
- 229910008291 Li—B—O Inorganic materials 0.000 claims description 2
- 229910007052 Li—Ti—O Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 5
- 239000002002 slurry Substances 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 5
- 239000005486 organic electrolyte Substances 0.000 abstract 1
- 229910020734 Li0.3La0.56TiO3 Inorganic materials 0.000 description 23
- 239000000463 material Substances 0.000 description 18
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 description 7
- 239000011268 mixed slurry Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-rate lithium manganate positive electrode material and a preparation method thereof. The preparation method comprises the following steps: firstly, carrying out high-energy ball milling on a lithium source and a manganese source, and then carrying out heat treatment to obtain spinel lithium manganate. Then carrying out high-energy ball milling with the solid electrolyte, and then carrying out heat treatment to coat the solid electrolyte. And stirring the coated lithium manganate and a high-molecular polymer aqueous solution to form uniform slurry, carrying out spray drying, and carrying out heat treatment to remove high molecules so as to form pores, thus obtaining the high-rate lithium manganate positive electrode material. The cathode material can effectively reduce the solubility of manganese in organic electrolyte, improve the conductivity of lithium ions and has high-rate cycle performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-rate lithium manganate positive electrode material and a preparation method thereof.
Background
Spinel lithium manganate LiMn2O4The cathode material has the advantages of rich manganese source, low cost, stable structure, high safety and the like, and is one of the favored cathode materials of the lithium ion battery. But due to Mn of the surface of lithium manganate at the end stage of discharge3+High concentration and easy disproportionation to generate Mn soluble in electrolyte2+And an electrolytic lithium salt LiPF6The generated small amount of HF can corrode the lithium manganate to cause the loss of manganese element, so that the capacity attenuation is fast. In addition, the conductivity of lithium manganate is also low. Both are not favorable for the large rate circulation of lithium manganate. Therefore, the lithium ion battery is not suitable for the lithium ion battery which is applied to the electric automobile by taking quick charge as a strategy at present.
It has been studied to coat spinel lithium manganate with silica, alumina, etc., which can suppress the loss of manganese, but these coating materials have poor conductivity and cannot provide a good conductive environment. In recent years, solid electrolytes have been studied greatly. Some solid electrolytes are not sensitive to water and oxygen, can exist in the air for a long time, have considerable lithium ion conductivity and wide electrochemical window, and provide a new idea for preparing electrode materials. Therefore, people begin to try to coat a layer of solid electrolyte on spinel lithium manganate by a sol-gel method; however, the sol-gel method is adopted to coat the solid electrolyte, so that the energy density is not high. Meanwhile, the coating is carried out by adopting a sol-gel method, and certain problems exist in industrial application.
Disclosure of Invention
The invention aims at the defects of the prior art; a high-rate porous microspherical lithium manganate positive electrode material is designed, and a set of preparation method matched with the high-rate porous microspherical lithium manganate positive electrode material is designed.
The invention relates to a high-rate lithium manganate positive electrode material; the high-rate lithium manganate cathode material is prepared from spinel lithium manganate LiMn2O4And a solid state electrolyte composition; the spinel lithium manganate LiMn2O4The solid electrolyte exists between the primary particles and on the surface of the secondary particles, and is in the form of porous microspheres.
In the high-rate lithium manganate positive electrode material, the mass fraction of the solid electrolyte is 1-6%.
The invention relates to a high-rate lithium manganate positive electrode material; the lithium manganate LiMn prepared from spinel2O4The particle size of the porous microspheres formed by the solid electrolyte is 10-15 microns; preferably 11.5-12.5 microns.
The invention relates to a high-rate lithium manganate positive electrode material; preparing the high-rate lithium manganate positive electrode material and graphite into a 3200mAh soft package, and testing the discharge capacity of the soft package at 30C; the discharge capacity is 2985mAh-3130 mAh. Is far higher than the products in the prior art.
The invention relates to a preparation method of a high-rate lithium manganate positive electrode material; the method comprises the following steps:
step one
Ball-milling and coating the spinel lithium manganate by using a solid electrolyte; carrying out heat treatment after ball milling; obtaining the coated spinel lithium manganate;
step two
Mixing the coated spinel lithium manganate obtained in the step one with a high molecular polymer aqueous solution, and pulping; and then carrying out spray drying, and carrying out heat treatment to remove the high molecular polymer so as to form a hole, thereby obtaining the high-rate lithium manganate positive electrode material.
The invention relates to a preparation method of a high-rate lithium manganate positive electrode material; the preparation method of the spinel lithium manganate comprises the following steps: and carrying out high-energy ball milling on the lithium source and the manganese source, and then carrying out heat treatment to obtain the spinel lithium manganate. The rotating speed of the high-energy ball mill is 100-600 rpm, and the ball milling time is 12-28 h. The heat treatment comprises the following steps: calcining for 2-12 h at 400-1000 ℃ in an oxygen-containing atmosphere, preferably in an air atmosphere. Preferably, the lithium source and manganese source are LiMn2O4The mixture is proportioned according to the stoichiometric ratio. More preferably, the lithium source is at least one selected from lithium compounds such as lithium hydroxide, lithium acetate, lithium carbonate and lithium nitrate, the manganese source is manganese dioxide, manganese carbonate or manganese sesquioxide,
the invention relates to a preparation method of a high-rate lithium manganate positive electrode material; in the first step, the solid electrolyte is selected from La-Li-Ti-O system solid electrolyte (such as Li)0.3La0.56TiO3) Li-Al-Ti-P-O system solid electrolyte (e.g. Li)1.3Ti1.7Al0.3(PO4)3) Li-La-Ta-O system solid electrolyte (e.g. Li)5La3Ta2O12) Li-B-O system solid electrolyte (e.g. 3 Li)2O-B2O3) Li-Ti-Zr-P-O system solid electrolyte (such as LiTi)0.5Zr1.5(PO4)3) And at least one of an oxide and a phosphate system stably existing in the air.
The invention relates to a preparation method of a high-rate lithium manganate positive electrode material; in the first step, during ball milling coating, the ball milling rotation speed is controlled to be 100-600 rpm, and the ball milling time is 12-28 h.
The invention relates to a preparation method of a high-rate lithium manganate positive electrode material; in the first step, after ball milling and coating, calcining for 2-12 h at 400-1000 ℃ in an oxygen-containing atmosphere, preferably an air atmosphere. Namely, the heat treatment after ball milling coating comprises the following steps: calcining for 2-12 h at 400-1000 ℃ and preferably 700-850 ℃ in an oxygen-containing atmosphere, preferably in an air atmosphere.
The invention relates to a preparation method of a high-rate lithium manganate positive electrode material; in the second step, the high molecular polymer is at least one selected from water-soluble high molecular polymers such as polyvinylpyrrolidone and carboxymethylcellulose.
Preferably, in the aqueous solution of the high molecular polymer in the second step, the mass fraction of the high molecular polymer is 0.05% to 3%.
Preferably, in the second step, the coated spinel lithium manganate obtained in the first step and the high molecular polymer aqueous solution are mixed and pulped according to the solid-liquid mass ratio of 1:1.5-3, preferably 1: 2.
Preferably, in the second step, the inlet temperature of the spray drying is 200-350 ℃, and the outlet temperature is 85-130 ℃.
The invention relates to a preparation method of a high-rate lithium manganate positive electrode material; in the second step, the heat treatment is as follows: calcining for 2-12 h at 400-1000 ℃ and preferably 700-850 ℃ in an oxygen-containing atmosphere, preferably in an air atmosphere.
Principles and advantages
The invention designs a high-rate porous microspherical lithium manganate positive electrode material for the first time; the high-rate lithium manganate cathode material is prepared from spinel lithium manganate LiMn2O4And a solid state electrolyte composition; the spinel lithium manganate LiMn2O4The solid electrolyte exists between the primary particles and on the surface of the secondary particles, and is in the form of porous microspheres.
The invention adopts ball milling coating and spray drying process with high molecular polymer for the first time to prepare the product with excellent performance. The solid electrolyte is coated among primary particles and on the surface of secondary particles of spinel lithium manganate by ball milling and spray drying, and the particles are porous microspherical. The problem that the manganese element is lost in the circulation process is solved, the lithium ion conductivity is improved, and the high rate performance is enhanced. The preparation method is simple and feasible and is suitable for industrialization. Meanwhile, after optimization, the discharge capacity of 30C is up to 2985mAh-3130mAh, preferably 3000-3130mAh through the synergistic effect of the preparation parameters. Is far higher than the products in the prior art.
Drawings
FIG. 1 is a discharge capacity test chart of 30C obtained in examples 1 to 4 and comparative examples 1 and 2.
Detailed Description
The invention prepares the high-rate lithium manganate cathode material by a ball milling method and a spray drying method. The following is a further description of the embodiments.
Example 1:
firstly, lithium carbonate and manganese dioxide are mixed into LiMn2O4The raw materials are mixed by a high-speed ball mill, the ball milling speed is 400rpm, and the ball milling time is 18 h. And (3) putting the ball-milled material into a crucible, preserving the heat for 8 hours at 500 ℃, and naturally cooling in a furnace. Thus obtaining the spinel lithium manganate.
Further according to LiMn2O45% by mass of solid electrolyte Li0.3La0.56TiO3. Mixing Li0.3La0.56TiO3Mixing with lithium manganate, and mixing the raw materials by using a high-speed ball mill, wherein the ball milling speed is 400rpm, and the ball milling time is 18 h. And (3) putting the ball-milled material into a crucible, preserving the heat for 4 hours at 500 ℃, and naturally cooling in a furnace. Namely to obtain Li0.3La0.56TiO3And (3) coated spinel lithium manganate.
500g of Li0.3La0.56TiO3And mixing the coated spinel lithium manganate with 1000g of carboxymethyl cellulose aqueous solution with the mass fraction of 1.5%, and stirring to obtain uniform slurry. And (3) carrying out spray drying treatment on the uniformly mixed slurry, wherein the inlet temperature is 350 ℃, and the outlet temperature is 120 ℃. The precursor is calcined at 800 ℃ for 4h to remove carboxymethyl cellulose, thereby forming pores. Namely to obtain Li0.3La0.56TiO3And (3) coating spinel lithium manganate porous microspheres. The prepared material and graphite are prepared into a soft package of 3200mAh, the discharge capacity of the soft package at 30C is tested, and the discharge capacity is 3126.9 mAh.
Example 2:
firstly, lithium carbonate and manganese dioxide are mixed into LiMn2O4Is weighed in a stoichiometric ratio and then is subjected to high-speed ball millingThe raw materials are mixed, the ball milling speed is 100rpm, and the ball milling time is 28 h. And (3) putting the ball-milled material into a crucible, preserving the heat for 8 hours at 1000 ℃, and naturally cooling in a furnace. Thus obtaining the spinel lithium manganate.
Further according to LiMn2O41% by mass of solid electrolyte Li0.3La0.56TiO3. Mixing Li0.3La0.56TiO3Mixing with lithium manganate, and mixing the raw materials by using a high-speed ball mill, wherein the ball milling speed is 100rpm, and the ball milling time is 12 hours. And (3) putting the ball-milled material into a crucible, preserving the heat for 12 hours at 400 ℃, and naturally cooling in a furnace. Namely to obtain Li0.3La0.56TiO3And (3) coated spinel lithium manganate.
500g of Li0.3La0.56TiO3And mixing the coated spinel lithium manganate with 1000g of carboxymethyl cellulose aqueous solution with the mass fraction of 0.05%, and stirring to obtain uniform slurry. And (3) carrying out spray drying treatment on the uniformly mixed slurry, wherein the inlet temperature is 200 ℃, and the outlet temperature is 85 ℃. The precursor is calcined at 400 ℃ for 12h to remove carboxymethyl cellulose, thereby forming pores. Namely to obtain Li0.3La0.56TiO3And (3) coating spinel lithium manganate porous microspheres. The prepared material and graphite are prepared into a soft package of 3200mAh, the discharge capacity of the soft package at 30C is tested, and the discharge capacity is 2987.6 mAh.
Example 3:
firstly, lithium carbonate and manganese dioxide are mixed into LiMn2O4The raw materials are mixed by a high-speed ball mill, the ball milling speed is 600rpm, and the ball milling time is 12 hours. And (3) putting the ball-milled material into a crucible, preserving the heat for 4 hours at 400 ℃, and naturally cooling in a furnace. Thus obtaining the spinel lithium manganate.
Further according to LiMn2O46% by mass of solid electrolyte Li0.3La0.56TiO3. Mixing Li0.3La0.56TiO3Mixing with lithium manganate, and mixing the raw materials by using a high-speed ball mill, wherein the ball milling speed is 600rpm, and the ball milling time is 28 h. Placing the ball-milled material into a crucible, and keeping the temperature at 1000 DEG CAnd (3) naturally cooling in the furnace. Namely to obtain Li0.3La0.56TiO3And (3) coated spinel lithium manganate.
500g of Li0.3La0.56TiO3And mixing the coated spinel lithium manganate with 1000g of carboxymethyl cellulose aqueous solution with the mass fraction of 3%, and stirring to obtain uniform slurry. And (3) carrying out spray drying treatment on the uniformly mixed slurry, wherein the inlet temperature is 350 ℃, and the outlet temperature is 130 ℃. And calcining the precursor at 1000 ℃ for 2h to remove carboxymethyl cellulose so as to form pores. Namely to obtain Li0.3La0.56TiO3And (3) coating spinel lithium manganate porous microspheres. The prepared material and graphite are prepared into a soft package of 3200mAh, the discharge capacity of the soft package at 30C is tested, and the discharge capacity is 2988.6 mAh.
Example 4:
firstly, lithium carbonate and manganese dioxide are mixed into LiMn2O4The raw materials are mixed by a high-speed ball mill, the ball milling speed is 400rpm, and the ball milling time is 20 hours. And (3) putting the ball-milled material into a crucible, preserving the heat for 7 hours at 700 ℃, and naturally cooling in a furnace. Thus obtaining the spinel lithium manganate.
Further according to LiMn2O43.5% by mass of solid electrolyte Li0.3La0.56TiO3. Mixing Li0.3La0.56TiO3Mixing with lithium manganate, and mixing the raw materials by using a high-speed ball mill, wherein the ball milling speed is 400rpm, and the ball milling time is 20 hours. And (3) putting the ball-milled material into a crucible, preserving the heat for 7 hours at 700 ℃, and naturally cooling in a furnace. Namely to obtain Li0.3La0.56TiO3And (3) coated spinel lithium manganate.
500g of Li0.3La0.56TiO3And mixing the coated spinel lithium manganate with 1000g of carboxymethyl cellulose aqueous solution with the mass fraction of 1.5%, and stirring to obtain uniform slurry. And (3) carrying out spray drying treatment on the uniformly mixed slurry, wherein the inlet temperature is 275 ℃, and the outlet temperature is 108 ℃. The precursor is calcined at 700 ℃ for 7h to remove carboxymethyl cellulose, thereby forming pores. Namely to obtain Li0.3La0.56TiO3And (3) coating spinel lithium manganate porous microspheres. The prepared material and graphite are prepared into a soft package of 3200mAh, the discharge capacity of the soft package at 30C is tested, and the discharge capacity is 3078.4 mAh.
Comparative example 1:
mixing lithium carbonate and manganese dioxide according to LiMn2O4The raw materials are mixed by a high-speed ball mill, the ball milling speed is 400rpm, and the ball milling time is 20 hours. And (3) putting the ball-milled material into a crucible, preserving the heat for 7 hours at 700 ℃, and naturally cooling in a furnace. Thus obtaining the spinel lithium manganate. The prepared material and graphite are prepared into a soft package of 3200mAh, the discharge capacity of the soft package at 30C is tested, and the discharge capacity is 783.7 mAh.
Comparative example 2
Mixing lithium carbonate and manganese dioxide according to LiMn2O4The raw materials are mixed by a high-speed ball mill, the ball milling speed is 400rpm, and the ball milling time is 20 hours. And (3) putting the ball-milled material into a crucible, preserving the heat for 7 hours at 700 ℃, and naturally cooling in a furnace. Thus obtaining the spinel lithium manganate.
Further according to LiMn2O45% by mass of solid electrolyte Li0.3La0.56TiO3. Mixing Li0.3La0.56TiO3Mixing with lithium manganate, and mixing the raw materials by using a high-speed ball mill, wherein the ball milling speed is 400rpm, and the ball milling time is 18 h. And (3) putting the ball-milled material into a crucible, preserving the heat for 4 hours at 500 ℃, and naturally cooling in a furnace. Namely to obtain Li0.3La0.56TiO3And (3) coated spinel lithium manganate.
The prepared material and graphite are prepared into a soft package of 3200mAh, and the discharge capacity of the soft package at 30C is tested, and the discharge capacity is only 1770.7 mAh.
Claims (9)
1. A high-rate lithium manganate positive electrode material; the method is characterized in that: the high-rate lithium manganate cathode material is prepared from spinel lithium manganate LiMn2O4And a solid state electrolyte composition; the spinel lithium manganate LiMn2O4Having a solid electrolyte between primary particles and on the surface of the secondary particlesAnd is porous microspherical;
the high-rate lithium manganate positive electrode material is prepared by the following steps:
step one
Ball-milling and coating the spinel lithium manganate by using a solid electrolyte; carrying out heat treatment after ball milling; obtaining the coated spinel lithium manganate;
step two
Mixing the coated spinel lithium manganate obtained in the step one with a high molecular polymer aqueous solution, and pulping; and then carrying out spray drying, and carrying out heat treatment to remove the high molecular polymer so as to form a hole, thereby obtaining the high-rate lithium manganate positive electrode material.
2. The high-rate lithium manganate positive electrode material of claim 1, wherein: the mass fraction of solid electrolyte in the high-rate lithium manganate positive electrode material is 1-6%.
3. The high-rate lithium manganate positive electrode material of claim 1, wherein: the lithium manganate LiMn prepared from spinel2O4And the particle size of the porous microspheres formed by the solid electrolyte is 10-15 microns.
4. The high-rate lithium manganate positive electrode material of claim 1, wherein: preparing the high-rate lithium manganate positive electrode material and graphite into a 3200mAh soft package, and testing the discharge capacity of the soft package at 30C; the discharge capacity is 2985mAh-3130 mAh.
5. The high-rate lithium manganate positive electrode material according to claim 1; the method is characterized in that: the preparation method of the spinel lithium manganate comprises the following steps: carrying out high-energy ball milling on a lithium source and a manganese source, and then carrying out heat treatment to obtain spinel lithium manganate;
the rotation speed of the high-energy ball mill is 100-600 rpm, and the ball milling time is 12-28 h;
the heat treatment comprises the following steps: calcining for 2-12 h at 400-1000 ℃ in an oxygen-containing atmosphere.
6. The high-rate lithium manganate positive electrode material according to claim 1; the method is characterized in that: in the first step, the solid electrolyte is at least one selected from La-Li-Ti-O system solid electrolyte, Li-Al-Ti-P-O system solid electrolyte, Li-La-Ta-O system solid electrolyte, Li-B-O system solid electrolyte and Li-Ti-Zr-P-O system solid electrolyte.
7. The high-rate lithium manganate positive electrode material according to claim 1; the method is characterized in that:
in the first step, during ball milling coating, the ball milling rotating speed is controlled to be 100-600 rpm, and the ball milling time is 12-28 h;
in the first step, after ball milling and coating, calcining for 2-12 hours at 400-1000 ℃ in an oxygen-containing atmosphere.
8. The high-rate lithium manganate positive electrode material according to claim 1; the method is characterized in that: in the second step, the high molecular polymer is at least one selected from polyvinylpyrrolidone and carboxymethyl cellulose;
in the aqueous solution of the high molecular polymer in the second step, the mass fraction of the high molecular polymer is 0.05-3%;
in the second step, the coated spinel lithium manganate obtained in the first step and a high molecular polymer aqueous solution are mixed and pulped according to the solid-liquid mass ratio of 1: 1.5-3.
9. The high-rate lithium manganate positive electrode material according to claim 1; the method is characterized in that:
in the second step, the inlet temperature of spray drying is 200-350 ℃, and the outlet temperature is 85-130 ℃;
in the second step, the heat treatment is as follows: calcining for 2-12 h at 400-1000 ℃ in an oxygen-containing atmosphere.
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