CN115241425B - Lithium manganate positive electrode material and preparation method thereof - Google Patents
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 43
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011247 coating layer Substances 0.000 claims abstract description 19
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims abstract description 10
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical group [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 26
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 12
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 6
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910015243 LiMg Inorganic materials 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical group [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052738 indium Inorganic materials 0.000 abstract description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 abstract description 5
- 239000011777 magnesium Substances 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 10
- 239000010405 anode material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium batteries, in particular to a lithium manganate positive electrode material and a preparation method thereof, wherein the lithium manganate positive electrode material comprises a core body and a coating layer, the coating layer is carbon-nitrogen co-doped strontium titanate, the core body is at least one doped lithium manganate of magnesium and indium, and the prepared lithium manganate positive electrode material has higher initial discharge specific capacity, excellent multiplying power performance, and good circulating performance, wherein the capacity retention rate is more than or equal to 97% after the lithium manganate positive electrode material circulates for 200 times at room temperature 1C multiplying power.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a lithium manganate positive electrode material and a preparation method thereof.
Background
With the increasing tension of traditional non-renewable energy sources such as petroleum, natural gas and the like and the increasing awareness of environmental protection, lithium ion batteries are receiving extensive attention as the green energy source most likely to replace petroleum at present. The lithium manganate has the advantages of three-dimensional tunnel structure, better lithium removal property, no toxicity of manganese, rich resources, high discharge voltage, long cycle life, simple synthesis process, overcharge resistance, safety performance and the like, and is recognized as a preferred positive electrode material for realizing large-scale application of the lithium ion power battery.
However, the problems of Jahn-Teller effect, dissolution of manganese, decomposition of electrolyte and the like of lithium manganate are easy to occur in the charge-discharge process, so that the cycle performance of the lithium manganate is continuously deteriorated, and in some research works which are carried out at present, surface coating and element doping are two common methods, but the effect is not ideal, other methods capable of improving the electrochemical performance of the lithium manganate are explored, and the method has great significance in promoting the application of the lithium manganate cathode material in lithium ion batteries.
Disclosure of Invention
The invention aims to: aiming at the technical problems, the invention provides a lithium manganate positive electrode material and a preparation method thereof.
The technical scheme adopted is as follows:
the lithium manganate positive electrode material comprises a core body and a coating layer, wherein the coating layer is carbon-nitrogen co-doped strontium titanate, and the core body is at least one doped lithium manganate of magnesium and indium.
Further, the core body is lithium manganate co-doped with magnesium and indium.
Further, the molecular formula of the lithium manganate is LiMg x In y Mn (2-x-y) O 4 X is 0.005-0.01, and y is 0.06-0.1.
Further, x is 0.006-0.009 and y is 0.065-0.08.
Further, x is 0.008 and y is 0.065.
Further, the preparation method of the nucleus comprises the following steps:
mixing magnesium nitrate solution and indium nitrate solution uniformly, adding lithium hydroxide and citric acid, heating to 40-50 ℃, stirring for 20-30min, adding manganese acetate solution, regulating pH of the system to be neutral by ammonia water, continuously stirring for 8-12h, drying the obtained gel at 100-120 ℃ for 10-15h, heating to 450-500 ℃ for roasting for 2-4h under the protection of argon, and heating to 800-850 ℃ for 10-20h in the second stage.
Further, the amounts of the lithium hydroxide and citric acid materials are the same.
Further, the first stage heating speed is 10-20 ℃/min, and the second stage heating speed is 1-5 ℃/min.
The invention also provides a preparation method of the lithium manganate anode material, which comprises the following steps:
adding strontium nitrate, phenylenediamine and tetraisopropyl titanate into isopropanol, stirring and mixing uniformly, regulating the pH of the system to 9-10 by using ammonia water, adding the nucleus, continuously stirring for 30-60min, removing the solvent by reduced pressure distillation, heating to 400-450 ℃ under the protection of the obtained solid argon, roasting for 3-5h, and heating to 800-850 ℃ and roasting for 30-40 min.
Further, the usage amount of the phenylenediamine is 3-6% of the mass of the strontium nitrate.
The invention has the beneficial effects that:
the invention provides a lithium manganate anode material, which replaces Mn after being doped with magnesium and indium 3+ Active ion Mn is reduced 3+ At the same time, the average oxidation state of manganese ions is increased, and Mn 4+ Has an ionic radius smaller than Mn 3+ Thus, the Mn-O bond length is shortened, the unit cell is contracted, the bond energy is improved, the structural stability of the crystal is enhanced, the Jahn-Teller effect is inhibited, and the crystal is moreThe method is favorable for the deintercalation of lithium ions in crystal lattices and is not easy to generate crystal lattice collapse in charge-discharge cycle, so that after magnesium and indium doping is carried out, the cycle performance is obviously improved, strontium titanate co-doped with carbon and nitrogen is taken as a coating layer, electrolyte can be effectively prevented from being in direct contact with active substances in positive electrode materials, corrosion on the positive electrode materials is relieved, and therefore the structural stability of the materials is improved, electrode polarization of the materials can be reduced by coating, the diffusion rate of lithium ions is improved, the cycle performance of the positive electrode materials is improved, the conductivity of the positive electrode materials can be improved by co-doping of carbon and nitrogen, the charge transfer between the electrodes and the electrolyte is promoted, and Li is improved + The lithium manganate positive electrode material prepared by the method has higher initial discharge specific capacity and excellent multiplying power performance, and the capacity retention rate is more than or equal to 97% after the lithium manganate positive electrode material is cycled for 200 times at room temperature 1C multiplying power, and the cycle performance is good.
Drawings
Fig. 1 is a TEM image of the lithium manganate cathode material prepared in example 1 of the present invention.
Detailed Description
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
the lithium manganate anode material comprises a core body and a coating layer, wherein the coating layer is carbon-nitrogen co-doped strontium titanate, and the core body is magnesium-indium co-doped lithium manganate.
The preparation method comprises the following steps:
mixing 500mL of 0.008mol/L magnesium nitrate solution and 500mL of 0.065mol/L indium nitrate solution uniformly, adding 500mL of 1.05mol/L lithium hydroxide and 100.87g of citric acid, heating to 50 ℃, stirring for 30min, adding 500mL of 1.927mol/L manganese acetate solution, regulating pH of the system to be neutral by ammonia water, continuing stirring for 10h, drying the obtained gel at 120 ℃ for 15h, heating to 480 ℃ for roasting for 4h at a speed of 15 ℃/min under the protection of argon, and heating to 850 ℃ for 20h at a second stage at a speed of 1 ℃/min to obtain LiMg molecular formula 0.008 In 0.065 Mn 1.927 O 4 Adding 366.9g of strontium nitrate, 20g of phenylenediamine and 568.4g of tetraisopropyl titanate into 4.8L of isopropanol, stirring and uniformly mixing, regulating the pH of the system to 10 by using ammonia water, adding the core, continuously stirring for 60min, distilling under reduced pressure to remove the solvent, heating to 450 ℃ under the protection of the obtained solid argon, roasting for 3h, and heating to 850 ℃ for 30-40 min.
Example 2:
the lithium manganate anode material comprises a core body and a coating layer, wherein the coating layer is carbon-nitrogen co-doped strontium titanate, and the core body is magnesium-indium co-doped lithium manganate.
The preparation method comprises the following steps:
mixing 500mL of 0.008mol/L magnesium nitrate solution and 500mL of 0.065mol/L indium nitrate solution uniformly, adding 500mL of 1.05mol/L lithium hydroxide and 100.87g of citric acid, heating to 50 ℃, stirring for 20min, adding 500mL of 1.927mol/L manganese acetate solution, regulating pH of the system to be neutral by ammonia water, continuing stirring for 12h, drying the obtained gel at 100 ℃ for 15h, heating to 500 ℃ for one stage at a speed of 10 ℃/min under the protection of argon gas, and heating to 800 ℃ for 20h at a second stage at a speed of 5 ℃/min to obtain LiMg 0.008 In 0.065 Mn 1.927 O 4 Adding 366.9g of strontium nitrate, 11g of phenylenediamine and 568.4g of tetraisopropyl titanate into 4.8L of isopropanol, stirring and uniformly mixing, regulating the pH of the system to 10 by using ammonia water, adding the core, continuously stirring for 30min, distilling under reduced pressure to remove the solvent, heating to 450 ℃ under the protection of the obtained solid argon, roasting for 3h, and heating to 850 ℃ for 30 min.
Example 3:
the lithium manganate anode material comprises a core body and a coating layer, wherein the coating layer is carbon-nitrogen co-doped strontium titanate, and the core body is magnesium-indium co-doped lithium manganate.
The preparation method comprises the following steps:
after 500mL of a magnesium nitrate solution of 0.008mol/L and 500mL of an indium nitrate solution of 0.065mol/L are mixed uniformly, 500mL of lithium hydroxide of 1.05mol/L and 100.87g of citric acid are added, the temperature is raised to 40 ℃ and stirred for 30min, 500mL of a manganese acetate solution of 1.927mol/L is added, and ammonia is usedAfter regulating the pH value of the system to be neutral by water, continuously stirring for 8 hours, drying the obtained gel at 120 ℃ for 10 hours, under the protection of argon, firstly heating to 450 ℃ for 4 hours at a speed of 20 ℃/min, and then heating to 850 ℃ for 10 hours at a speed of 1 ℃/min to obtain the LiMg with the molecular formula of 0.008 In 0.065 Mn 1.927 O 4 Adding 366.9g of strontium nitrate, 22g of phenylenediamine and 568.4g of tetraisopropyl titanate into 4.8L of isopropanol, stirring and uniformly mixing, regulating the pH of the system to 9 by using ammonia water, adding the core, continuously stirring for 60min, removing the solvent by reduced pressure distillation, heating to 400 ℃ under the protection of the obtained solid argon, roasting for 5h, and heating to 800 ℃ for 40 min.
Example 4:
the lithium manganate anode material comprises a core body and a coating layer, wherein the coating layer is carbon-nitrogen co-doped strontium titanate, and the core body is magnesium-doped lithium manganate.
The preparation method was substantially the same as in example 1, except that the indium nitrate solution was not added during the preparation.
Example 5:
the lithium manganate anode material comprises a core body and a coating layer, wherein the coating layer is carbon-nitrogen co-doped strontium titanate, and the core body is indium-doped lithium manganate.
The preparation was substantially the same as in example 1, except that the magnesium nitrate solution was not added during the preparation.
Comparative example 1:
substantially the same as in example 1, except that the core body was lithium manganate.
Comparative example 2:
substantially the same as in example 1, except that the coating layer was not contained.
Comparative example 3:
substantially the same as in example 1, except that the coating layer was strontium titanate.
Performance test:
the lithium manganate positive electrode materials prepared in the examples 1-5 and the comparative examples 1-3, the conductive agent (SP) and the adhesive (PVDF) are mixed according to the mass ratio of 8:1:1, adding a proper amount of NMP as a solvent, ball milling for 5 hours to obtain a uniform mixture, uniformly coating the uniform mixture on an aluminum foil through a coater, wherein the coating thickness is 125um, placing the coated aluminum foil in an oven, drying at 95 ℃, then cutting the aluminum foil by a sheet punching machine to obtain a positive electrode sheet, placing the obtained positive electrode sheet in a vacuum drying oven, maintaining at 105 ℃ for 10 hours to remove moisture therein, transferring the positive electrode sheet into the glove box for battery assembly, wherein the assembled battery is a button half battery, the model is CR-2032, the positive electrode is the prepared positive electrode sheet, the negative electrode is a metal lithium sheet, the diaphragm is a Celgard2400 polypropylene microporous membrane, the electrolyte is 1mol/L lithium hexafluorophosphate (LiPF) Ethylene Carbonate (EC) +methyl ethyl carbonate (EMC) +dimethyl carbonate (DMC) (volume ratio is 1:1), and standing for 12 hours, and performing electrochemical tests.
Constant current charge and discharge tests are carried out on the button half batteries by using a LandCT2001A battery test system, and the quick charge and quick discharge performance can be measured by a multiplying power performance test, and specific test conditions are as follows: the voltage range is 3.5-5V (vs. Li + Li), test rates of 0.2C, 0.5C, 1C, 2C, 3C, and 5C (1c=140 mA/g), test temperatures of 25 ℃, test results are shown in table 1 below:
and (3) performing cyclic voltammetry test on the button half cell by using an interface 000 type electrochemical workstation, wherein the test conditions are as follows: the voltage range was 3.5-5V, the scan rate was 0.1mV/s, the test temperature was 25℃and the capacity retention after 200 cycles at 1C rate was tested, the test results are shown in Table 2 below:
table 1:
table 2:
| capacity retention/% | |
| Example 1 | 98.9 |
| Example 2 | 98.3 |
| Example 3 | 98.6 |
| Example 4 | 97.4 |
| Example 5 | 97.1 |
| Comparative example 1 | 94.2 |
| Comparative example 2 | 93.9 |
| Comparative example 3 | 97.3 |
As can be seen from the above tables 1 and 2, the lithium manganate positive electrode material prepared by the invention has higher initial discharge specific capacity, excellent multiplying power performance, and good cycle performance, and the capacity retention rate is more than or equal to 97% after the lithium manganate positive electrode material is cycled for 200 times at room temperature and 1C multiplying power.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (3)
1. The lithium manganate positive electrode material is characterized by comprising a core body and a coating layer, wherein the coating layer is carbon-nitrogen co-doped strontium titanate, and the core body is magnesium-indium co-doped lithium manganate;
the molecular formula of the lithium manganate is LiMg x In y Mn (2-x-y) O 4 X is 0.008 and y is 0.065;
the preparation method of the nucleus comprises the following steps:
uniformly mixing a magnesium nitrate solution and an indium nitrate solution, adding lithium hydroxide and citric acid, heating to 40-50 ℃, stirring for 20-30min, adding a manganese acetate solution, regulating the pH value of a system to be neutral by ammonia water, continuously stirring for 8-12h, drying the obtained gel at 100-120 ℃ for 10-15h, heating to 450-500 ℃ for roasting for 2-4h under the protection of argon, and heating to 800-850 ℃ for 10-20h in the second stage;
the preparation method of the lithium manganate positive electrode material comprises the following steps:
adding strontium nitrate, phenylenediamine and tetraisopropyl titanate into isopropanol, stirring and mixing uniformly, regulating the pH of the system to 9-10 by using ammonia water, adding the nucleus, continuously stirring for 30-60min, removing the solvent by reduced pressure distillation, heating to 400-450 ℃ under the protection of the obtained solid argon, roasting for 3-5h, and heating to 800-850 ℃ and roasting for 30-40 min.
2. The lithium manganate positive electrode material according to claim 1, wherein the amounts of substances of lithium hydroxide and citric acid are the same.
3. The lithium manganate positive electrode material according to claim 1, wherein the first stage temperature rise rate is 10-20 ℃/min and the second stage temperature rise rate is 1-5 ℃/min.
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| CN1298210A (en) * | 1999-11-30 | 2001-06-06 | 中国科学院成都有机化学研究所 | Cathode material for lithium ion battery and its making process |
| CN106252623A (en) * | 2016-08-26 | 2016-12-21 | 深圳博磊达新能源科技有限公司 | A kind of carbon-nitrogen doped lithium titanate electrode material, preparation method and application |
| CN109768268A (en) * | 2019-03-16 | 2019-05-17 | 湖南海利锂电科技股份有限公司 | Manganate cathode material for lithium and preparation method thereof |
| CN110247039A (en) * | 2019-06-17 | 2019-09-17 | 启东启澳新材料科技发展有限公司 | A kind of nickel lithium manganate cathode material preparation method coating strontium titanate base conductive coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298210A (en) * | 1999-11-30 | 2001-06-06 | 中国科学院成都有机化学研究所 | Cathode material for lithium ion battery and its making process |
| CN106252623A (en) * | 2016-08-26 | 2016-12-21 | 深圳博磊达新能源科技有限公司 | A kind of carbon-nitrogen doped lithium titanate electrode material, preparation method and application |
| CN109768268A (en) * | 2019-03-16 | 2019-05-17 | 湖南海利锂电科技股份有限公司 | Manganate cathode material for lithium and preparation method thereof |
| CN110247039A (en) * | 2019-06-17 | 2019-09-17 | 启东启澳新材料科技发展有限公司 | A kind of nickel lithium manganate cathode material preparation method coating strontium titanate base conductive coating |
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