CN114132966A - Surface-modified lithium manganate material and preparation method thereof - Google Patents
Surface-modified lithium manganate material and preparation method thereof Download PDFInfo
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- CN114132966A CN114132966A CN202010918178.XA CN202010918178A CN114132966A CN 114132966 A CN114132966 A CN 114132966A CN 202010918178 A CN202010918178 A CN 202010918178A CN 114132966 A CN114132966 A CN 114132966A
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical class [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 55
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000004576 sand Substances 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 238000002386 leaching Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 claims description 3
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 229910000659 lithium lanthanum titanates (LLT) Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000011888 foil Substances 0.000 description 12
- 239000011267 electrode slurry Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a surface-modified lithium manganate material and a preparation method thereof, and is characterized in that: adding lithium-containing solid electrolyte, a dispersing agent, a metal leaching agent and water into a sand mill, and fully grinding the mixture and zirconia balls together to ensure that the solid electrolyte is nanocrystallized and a small amount of metal ions are leached out to obtain nano solid electrolyte slurry, wherein the mass of the metal leaching agent is 0.5-2% of that of the solid electrolyte; mixing lithium manganate with nano solid electrolyte slurry, drying, and sintering at high temperature in an inert atmosphere to obtain a surface-modified lithium manganate positive electrode material; wherein the mass of the solid electrolyte in the nano solid electrolyte slurry is 1-3% of that of the lithium manganate, and the high-temperature sintering temperature is 350-600 ℃. The method is simple, low in cost, good in product consistency and easy to industrialize, and the prepared lithium manganate positive electrode material has good lithium ion transmission channels and electronic channels and good high-temperature cyclicity.
Description
Technical Field
The invention relates to a lithium manganate material for a lithium ion battery, in particular to a surface modified lithium manganate material and a preparation method thereof.
Background
The lithium manganate is used as the anode material of the lithium ion battery and has the advantages of rich resources, low cost, high voltage, good safety, high volume energy density and the like. At present, lithium manganate has been widely used in lithium ion batteries for electric bicycles and other low-speed electric vehicles. However, the lithium manganate battery has poor cycle performance and insufficient high-temperature stability, and is difficult to meet the service life and use requirements of automobile-grade batteries, so that the lithium manganate battery has a low occupation ratio in the field of lithium ion batteries for new energy automobiles. The main reason for the above problems is that the lithium manganate has low conductivity, is easily polarized during charge and discharge at high rate, low temperature and final stage of discharge, and generates much Mn3+，Mn3+Easily disproportionate to generate soluble Mn2+And deposit on the surface of the negative electrode under the action of a potential, thereby blocking a lithium ion diffusion channel and causing the attenuation of the battery capacity.
The surface modification of lithium manganate is an effective method for improving the performance of lithium ion batteries. In the prior art, the most commonly used method is to dope other transition metal ions to inhibit manganese dissolution. Chinese patent publication No. CN103022467A discloses a surface-treated lithium manganate material and a preparation method thereof, wherein a Ti-containing organic substance or an Al-containing organic substance is used as a surface-treated material, the doped and modified lithium manganate is added into a solution or suspension of the surface-treated material, and is dried by a spray drying method after being uniformly stirred, and then is subjected to heat treatment, so as to obtain a surface-modified metal ion lithium manganate material. The method improves the high-temperature storage and high-temperature cycle performance of the lithium manganate material, but the used metal organic salt is expensive, the spray drying energy consumption is high, the industrial production is difficult, and the method only improves the stability of the lithium manganate through surface inhibition, does not substantially improve the transmission property of lithium ions, and still has the polarization phenomenon.
The Chinese patent application with the publication number of CN101841022A discloses a method for preparing a Chinese patent medicineThe preparation method of lithium manganate as positive electrode material of lithium ion battery uses Li (CH)3COO)·2H2O and Al (NO)3)3·9H2And O, preparing a solution, adding the lithium manganate, drying and sintering to obtain the lithium manganate coated with the solid electrolyte on the surface.
The Chinese patent application with publication number CN109004212A discloses a high-rate lithium manganate positive electrode material and a preparation method thereof, wherein spinel lithium manganate and solid electrolyte are subjected to high-energy ball milling and then subjected to heat treatment to coat the solid electrolyte, and a high-molecular polymer is adopted for mixing, then spray drying and heat treatment are carried out to obtain the porous high-rate lithium manganate positive electrode material. The method improves the rate capability of the lithium manganate, but the high molecular polymer adopted for pore forming has higher cost, and the ball mill can only ball-mill particles to micron level, so that effective coating cannot be carried out.
Therefore, a new method for effectively improving the spinel lithium manganate material is needed to overcome the above technical problems and cost problems, and obtain a lithium ion battery cathode material with excellent performance, stability and easy preparation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a surface-modified lithium manganate material, and the lithium manganate positive electrode material has good high-temperature cyclicity, simple preparation method, low cost, good product consistency and easy industrialization.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a preparation method of a surface-modified lithium manganate material is characterized by comprising the following steps:
(1) adding lithium-containing solid electrolyte, a dispersing agent, a metal leaching agent and water into a sand mill, fully grinding the lithium-containing solid electrolyte, the dispersing agent, the metal leaching agent and the water together with zirconia balls to enable the solid electrolyte to be nanocrystallized to obtain nano solid electrolyte slurry, wherein the mass of the metal leaching agent is 0.5-2% of that of the solid electrolyte;
(2) mixing lithium manganate with the nano solid electrolyte slurry obtained in the step (1), drying, and sintering at high temperature in an inert atmosphere to obtain a surface-modified lithium manganate positive electrode material; wherein the mass of the solid electrolyte in the nano solid electrolyte slurry is 1-3% of that of the lithium manganate, and the high-temperature sintering temperature is 350-600 ℃.
In the step (2), in the high-temperature sintering process, the dispersing agent is carbonized, the nano solid electrolyte is dispersed among lithium manganate particles and on the surfaces of the particles, and the dissolved metal ions permeate into the surfaces of the lithium manganate to form the surface-modified lithium manganate cathode material.
In the above technical solution, the solid electrolyte is one of Lithium Aluminum Titanium Phosphate (LATP), Lithium Lanthanum Zirconium Oxide (LLZO), and Lithium Lanthanum Titanate (LLTO).
In the above technical solution, the dispersant is one of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) and polyvinyl alcohol (PVA), the mass of PVP is preferably 15% of the mass of the solid electrolyte, the mass of PEG and PVA is preferably 20% of the mass of the solid electrolyte, and at this time, the mass of the dispersant after carbonization is about 10% of the mass of the solid electrolyte, which can meet the requirement of electron conductivity.
In the technical scheme, during sanding, the diameter of the zirconia ball is 0.3mm, the mass ratio of the zirconia ball to the material to water is 10: 1: 1, the rotating speed of the sanding machine is 2000r/min, and the grinding time is 30-120 minutes. The zirconia balls are small, the ball material ratio is high, the specific surface area of the balls is large, the contact grinding points of the balls are more, meanwhile, the rotational speed of the sand mill is high, the linear velocity is high, the kinetic energy obtained by the balls is large, the shearing, extruding and stripping capabilities are strong, and the solid electrolyte can be fully crushed.
In the above technical scheme, the metal dissolution reagent is hydrofluoric acid (HF) or nitric acid (HNO)3) And one of sodium hydroxide (NaOH), the mass of the solid electrolyte is preferably 1%, and after the solid electrolyte is sanded to be nanoscale, the specific surface is larger, so that the dissolving speed of metal ions is accelerated.
In the technical scheme, the lithium manganate is preferably spinel-phase single-crystal lithium manganate with the particle size of 8-12 microns.
In the above technical scheme, the addition amount of the solid electrolyte is less than 3% of the mass of the lithium manganate, and is preferably 1.2%. After the nano solid electrolyte is added, lithium ions can be transmitted between the surface of the lithium manganate and particles through the solid electrolyte, meanwhile, the electrolyte can be adsorbed by a large specific surface area, the circulation stability is ensured, but the content of active substances is influenced by too much addition amount, so that the specific capacity is reduced, and therefore, the preferable addition amount is 1.2%.
In the above technical scheme, the step (2) can adopt a mixing mode of sand milling, ball milling and stirring.
In the technical scheme, the inert atmosphere is argon or nitrogen, the high-temperature sintering temperature is 350-600 ℃, and the time is 4-12 hours. Under the inert atmosphere, the dispersing agent is carbonized, a conductive layer is formed between the surface of the lithium manganate and the particles, and the polarization of the lithium manganate is reduced.
The invention also discloses the surface-modified lithium manganate material obtained by the preparation method.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention creatively utilizes the metal ions dissolved out when the solid electrolyte is nanocrystallized to dope the surface of the lithium manganate material, and the purpose can be achieved only by adding cheap and easily obtained strong acid or strong base as a metal dissolving agent.
2. According to the invention, a lithium ion rapid channel is constructed, a nano solid electrolyte with a high specific surface area is added to form a lithium ion rapid migration channel, and meanwhile, the high specific surface area can adsorb the electrolyte, so that desolvation of lithium ions is enhanced, and the migration rate of the lithium ions is further improved.
3. The invention constructs an effective electronic channel, utilizes the dispersant added during the nanocrystallization of the solid electrolyte, and carbonizes the solid electrolyte through high-temperature treatment, thereby improving the electronic conductivity of the lithium manganate material, not only omitting the step of removing the dispersant, but also fully utilizing the value of the lithium manganate material.
4. The invention has wide applicability, can meet the requirements of different types of fast ion conductors, has high tolerance of preparation conditions and is convenient for production.
Drawings
Fig. 1 is a graph showing a particle size analysis of nano solid electrolyte slurry prepared in example 1.
Detailed Description
The invention is further described below with reference to the following examples:
example 1:
50g of LATP (lithium aluminum titanium phosphate) solid electrolyte, 7.5g of PVP (polyvinylpyrrolidone), 0.5g of HF and 58g of deionized water are weighed, added into a sand mill, put into 580g of 0.3mm zirconia balls, set the rotating speed of the sand mill to be 2000r/min and ground for 60 minutes to prepare the nano solid electrolyte slurry.
Adding 200g of single crystal lithium manganate and 5.6g of nano solid electrolyte slurry into a sand mill, grinding for 20 minutes at a ball-to-material ratio of 2:1, drying, placing in a tube furnace, and preserving heat for 6 hours at 550 ℃ under a nitrogen atmosphere to obtain the LATP surface modified lithium manganate material.
Mixing the obtained lithium manganate material with sp (carbon black conductive agent), CNTs (carbon nano tube conductive agent) and PVDF (polyvinylidene fluoride) according to the mass ratio of 95: 1: 2: 2, adding NMP (N-methyl pyrrolidone), stirring the mixture into anode slurry, uniformly coating the anode slurry on an aluminum foil, drying the aluminum foil for 6 hours at 80 ℃, drying the aluminum foil for 12 hours in vacuum at 120 ℃ to obtain a pole piece, transferring the pole piece into a glove box, and assembling the CR2032 type button cell by taking metal lithium as a counter electrode.
The battery manufactured according to the embodiment has the reversible capacity of 120.2 mAh/g at 0.2C multiplying power, still has 117.3 mAh/g after 100 cycles at 1C multiplying power at normal temperature, and still has 111.5 mAh/g after 100 cycles at 1C multiplying power at 45 ℃.
Example 2:
50g of LLZO (lithium lanthanum zirconium oxide), 10g of PEG (polyethylene glycol), 0.5g of NaOH and 60.5g of deionized water are weighed, added into a sand mill, 605g of 0.3mm zirconia balls are placed, and ground for 120 minutes to prepare the nano solid electrolyte slurry. Adding 200g of single-crystal lithium manganate and 14.52g of nano solid electrolyte slurry into a ball mill, wherein the ball-to-material ratio is 2:1, carrying out ball milling for 30 minutes, drying, placing in a tube furnace, and carrying out heat preservation for 4 hours at 600 ℃ under the argon atmosphere to obtain the LLZO surface modified lithium manganate material.
Mixing the obtained lithium manganate positive electrode material with sp, CNTs and PVDF according to the mass ratio of 95: 1: 2: 2, adding NMP, stirring the mixture into positive electrode slurry, uniformly coating the positive electrode slurry on an aluminum foil, drying the aluminum foil for 6 hours at 80 ℃, vacuum drying the aluminum foil for 12 hours at 120 ℃ to obtain a pole piece, transferring the pole piece into a glove box, and assembling the CR2032 type button cell by taking metal lithium as a counter electrode. The battery manufactured according to the embodiment has the reversible capacity of 110.1 mAh/g under the 0.2C multiplying power, still has 108.6 mAh/g after 100 cycles of 1C multiplying power at normal temperature, and still has 106.6 mAh/g after 100 cycles of 1C multiplying power at 45 ℃.
Example 3:
50g of LLTO (lanthanum lithium titanate), 10g of PVA (polyvinyl alcohol) and 0.5g of HNO were weighed out3And 60.5g of deionized water, adding the mixture into a sand mill, putting 605g of 0.3mm zirconia balls, and grinding for 30 minutes to prepare the nano solid electrolyte slurry. And (3) putting 200g of single-crystal lithium manganate and 7.26g of nano solid electrolyte slurry into a beaker, magnetically stirring at 600rpm for 60 minutes, drying, then putting into a tube furnace, and preserving heat at 350 ℃ for 12 hours under nitrogen atmosphere to obtain the LLTO surface modified lithium manganate material.
Mixing the obtained lithium manganate positive electrode material with sp, CNTs and PVDF according to the mass ratio of 95: 1: 2: 2, adding NMP, stirring the mixture into positive electrode slurry, uniformly coating the positive electrode slurry on an aluminum foil, drying the aluminum foil for 6 hours at 80 ℃, vacuum drying the aluminum foil for 12 hours at 120 ℃ to obtain a pole piece, transferring the pole piece into a glove box, and assembling the CR2032 type button cell by taking metal lithium as a counter electrode. The battery manufactured according to the embodiment has the reversible capacity of 118.3 mAh/g at 0.2C multiplying power, still has 115.3 mAh/g after 100 cycles at 1C multiplying power at normal temperature, and still has 111.9 mAh/g after 100 cycles at 1C multiplying power at 45 ℃.
Example 4:
50g of LATP, 7.5g of PVP, 0.5g of NaOH and 58g of deionized water are weighed, added into a sand mill, and 580g of 0.3mm zirconia balls are placed into the sand mill and ground for 120 minutes to prepare the nano solid electrolyte slurry. Adding 200g of single crystal lithium manganate and 13.92g of nano solid electrolyte slurry into a sand mill, grinding for 20 minutes at a ball-to-material ratio of 2:1, drying, placing in a tube furnace, and preserving heat for 12 hours at 600 ℃ under a nitrogen atmosphere to obtain the LATP surface modified lithium manganate material.
Mixing the obtained lithium manganate positive electrode material with sp, CNTs and PVDF according to the mass ratio of 95: 1: 2: 2, adding NMP, stirring the mixture into positive electrode slurry, uniformly coating the positive electrode slurry on an aluminum foil, drying the aluminum foil for 6 hours at 80 ℃, vacuum drying the aluminum foil for 12 hours at 120 ℃ to obtain a pole piece, transferring the pole piece into a glove box, and assembling the CR2032 type button cell by taking metal lithium as a counter electrode. The battery prepared according to the embodiment has the reversible capacity of 117.2 mAh/g at 0.2C multiplying power, still has 117.0 mAh/g after 100 cycles at 1C multiplying power at normal temperature, and still has 114.1 mAh/g after 100 cycles at 1C multiplying power at 45 ℃.
Claims (10)
1. A preparation method of a surface-modified lithium manganate material is characterized by comprising the following steps:
(1) adding lithium-containing solid electrolyte, a dispersing agent, a metal leaching agent and water into a sand mill, fully grinding the lithium-containing solid electrolyte, the dispersing agent, the metal leaching agent and the water together with zirconia balls to enable the solid electrolyte to be nanocrystallized to obtain nano solid electrolyte slurry, wherein the mass of the metal leaching agent is 0.5-2% of that of the solid electrolyte;
(2) mixing lithium manganate with the nano solid electrolyte slurry obtained in the step (1), drying, and sintering at high temperature in an inert atmosphere to obtain a surface-modified lithium manganate positive electrode material; wherein the mass of the solid electrolyte in the nano solid electrolyte slurry is 1-3% of that of the lithium manganate, and the high-temperature sintering temperature is 350-600 ℃.
2. The method for preparing the surface-modified lithium manganate material according to claim 1, characterized in that: the solid electrolyte is one of lithium aluminum titanium phosphate, lithium lanthanum zirconium oxide and lithium lanthanum titanate.
3. The method for preparing the surface-modified lithium manganate material according to claim 1, characterized in that: the dispersing agent is one of polyvinylpyrrolidone, polyethylene glycol and polyvinyl alcohol, and the mass of the dispersing agent is 15-20% of that of the solid electrolyte.
4. The method for preparing the surface-modified lithium manganate material according to claim 1, characterized in that: the metal stripping agent is one of hydrofluoric acid, nitric acid and sodium hydroxide, and the mass of the metal stripping agent is 1% of that of the solid electrolyte.
5. The method for preparing the surface-modified lithium manganate material according to claim 1, characterized in that: when sanding, the diameter of the zirconia ball is 0.3mm, the mass ratio of the zirconia ball to the materials to the water is 10: 1, the rotating speed of the sand mill is 2000r/min, and the grinding time is 30-120 minutes.
6. The method for preparing the surface-modified lithium manganate material according to claim 1, characterized in that: the lithium manganate in the step (2) is spinel-phase single-crystal lithium manganate with the particle size of 8-12 microns.
7. The method for preparing the surface-modified lithium manganate material according to claim 1, characterized in that: the addition amount of the solid electrolyte is 1.2 percent of the mass of the lithium manganate.
8. The method for preparing the surface-modified lithium manganate material according to claim 1, characterized in that: and (3) mixing in the step (2) is realized by adopting a sand grinding, ball milling or stirring mode.
9. The method for preparing the surface-modified lithium manganate material according to claim 1, characterized in that: the inert atmosphere is argon atmosphere or nitrogen atmosphere, and the high-temperature sintering time is 4-12 hours.
10. The surface-modified lithium manganate material obtained by the production method of any one of claims 1 to 9.
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