CN114394624B - Multistage porous monocrystalline micron-sized LiMn 2 O 4 Preparation method of positive electrode material - Google Patents
Multistage porous monocrystalline micron-sized LiMn 2 O 4 Preparation method of positive electrode material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 15
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 title claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000002696 manganese Chemical class 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000006228 supernatant Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 17
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical group [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical group [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 claims description 3
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 3
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical group O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 3
- 229910015645 LiMn Inorganic materials 0.000 claims 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 239000010405 anode material Substances 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- MSMNVXKYCPHLLN-UHFFFAOYSA-N azane;oxalic acid;hydrate Chemical compound N.N.O.OC(=O)C(O)=O MSMNVXKYCPHLLN-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- 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
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a multi-stage porous single-crystallization micron-sized LiMn 2 O 4 The preparation method of the positive electrode material comprises the following steps: firstly, adding manganese salt and lithium salt into deionized water, and stirring and dispersing uniformly to obtain a mixed solution A; adding polyethylene glycol and sodium dodecyl diphenyl ether disulfonate into the mixed solution A, and stirring and dispersing uniformly to obtain a mixed solution B; thirdly, adding ammonium salt into deionized water, and stirring and dispersing uniformly to obtain a mixed solution C; fourthly, adding the mixed solution C into the mixed solution B to obtain a mixed solution D; transferring the mixed solution D into a polytetrafluoroethylene-lined reaction kettle, performing hydrothermal reaction, cooling to room temperature after finishing, removing supernatant, performing centrifugal separation, and washing to obtain a precursor of lithium manganate; and step six, roasting the precursor of lithium manganate, and cooling to room temperature after the roasting is finished, so that the lithium ion battery anode material is assembled, and the specific capacity, the multiplying power performance and the cycle performance of the battery are improved.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a multi-stage porous single-crystallization micron-sized LiMn 2 O 4 A preparation method of a positive electrode material.
Background
At present, along with the development of society, low carbon and environmental protection become the global development trend, lithium ion batteries are used as renewable green and environmental-friendly chemical energy sources, have the performances of high specific capacity, high working voltage, long service life, no memory effect in charge and discharge and the like, and become hot spots of various researches. The lithium battery positive electrode material mainly produced in mass production on the market mainly comprises layered lithium cobalt oxide (LiCoO) 2 ) And ternary materials (Li (Ni) x Co y Mn z )O 2 ) Olivine structured lithium iron phosphate (LiFePO 4 ) And spinel structured lithium manganate (LiMn) 2 O 4 ). Wherein the theoretical specific capacity of spinel lithium manganate is 148mAh g -1 The lithium ion battery has the advantages of unique three-dimensional tunnel structure, contribution to the intercalation and deintercalation of lithium ions, higher power and energy density, rich raw material sources, low cost, overcharge resistance and environmental friendliness, is one of the positive electrode active materials which is most hopeful to replace lithium cobalt oxide, and has great development potential in the field of lithium ion power batteries.
However, the main problem of lithium manganate is that the capacity attenuation is large, the cycle life is short, and the capacity attenuation is serious especially in the high-temperature cycle and storage process. The reasons for capacity fade are mainly manganese dissolution, electrolyte decomposition and John-Teller effect. The dissolution of manganese has close relations with the crystal structure, crystallinity, primary particle size, morphology and the like of the lithium manganate material, and the specific capacity and the cycle performance of the electrode are directly affected.
In view of the above, it is necessary to provide a novel preparation method for obtaining multi-stage porous single-crystallized micron-sized LiMn 2 O 4 The lithium manganate prepared by the prior art is used for solving the problems of large capacity attenuation and short cycle life.
Disclosure of Invention
In order to solve the defects existing in the prior art, the invention aims to provide a novel preparation method for successfully preparing single-crystal LiMn with smooth surface, regular interface development and high crystallinity 2 O 4 And has a multi-stage porous microstructure. The lithium ion battery anode material is assembled, and the specific capacity, the multiplying power performance and the cycle performance of the battery are greatly improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
multistage porous monocrystalline micron-sized LiMn 2 O 4 The preparation method of the positive electrode material comprises the following steps:
adding manganese salt and lithium salt into deionized water, and stirring and dispersing uniformly to obtain a mixed solution A;
step two, adding polyethylene glycol and sodium dodecyl diphenyl ether disulfonate into the mixed solution A, and stirring and dispersing uniformly to obtain a mixed solution B;
adding ammonium salt into deionized water, and stirring and dispersing uniformly to obtain a mixed solution C;
step four, adding the mixed solution C into the mixed solution B to obtain a mixed solution D;
transferring the mixed solution D into a polytetrafluoroethylene lining reaction kettle, performing hydrothermal reaction, cooling to room temperature after finishing, removing supernatant, and performing centrifugal separation and washing to obtain a precursor of lithium manganate;
step six, roasting the precursor of lithium manganate, and cooling to room temperature after the roasting is finished to obtain the LiMn 2 O 4 And a positive electrode material.
Preferably, in the first step, the manganese salt is manganese acetate tetrahydrate; the lithium salt is lithium acetate dihydrate; the molar ratio of the manganese salt to the lithium salt is 1:2; the volume ratio of the manganese salt to the deionized water is 1.5:50.
Preferably, in the second step, the polyethylene glycol is polyethylene glycol-200; the molar ratio of the polyethylene glycol to the sodium dodecyl diphenyl ether disulfonate to the manganese salt is 1:1:15.
Preferably, in the third step, the ammonium salt is ammonium oxalate; the molar ratio of the ammonium salt to the manganese salt is 4:1; the volume ratio of the ammonium salt to deionized water is 1:5.
Preferably, the roasting in the fifth step specifically includes: in a program temperature control box type electric furnace, the temperature is raised to 200 ℃ from room temperature at a heating rate of 50 ℃/min, the reaction is kept for 6 hours, and the mixture is taken out and put into ice water to be quickly cooled to the room temperature.
Preferably, in the fifth step, the washing is performed three times with deionized water and absolute ethanol, respectively.
More preferably, the fifth step specifically includes: transferring the mixed solution D to a stainless steel reaction kettle with a polytetrafluoroethylene liner, sealing, placing in a program-controlled temperature box type electric furnace, quickly heating to 200 ℃ from room temperature at a heating rate of 50 ℃/min, preserving heat for 6 hours, taking out, placing in ice water, and quickly cooling to room temperature. Taking out the liner, pouring out the supernatant, adding deionized water, transferring to a centrifuge tube, centrifugally separating, and repeatedly washing with deionized water and absolute ethyl alcohol for three times respectively to obtain a precursor of the synthesized lithium manganate.
Preferably, the roasting in the sixth step specifically includes: in a program temperature control box type electric furnace, in an air atmosphere, heating the resistance furnace to 600 ℃ at a speed of 5 ℃/min, preheating for 6 hours, and then continuously heating to 900 ℃ at a speed of 3 ℃/min, and roasting for 12 hours.
More preferably, the sixth step specifically includes: and (3) putting the lithium manganate precursor into a quartz boat, and putting the quartz boat into a program temperature control box type electric furnace. In the air atmosphere, heating the resistance furnace at 5 ℃/min, preheating for 6 hours at 600 ℃, then heating at 3 ℃/min, continuously heating to 900 ℃ for roasting for 12 hours, and naturally cooling to obtain the multi-stage porous monocrystalline micron-sized LiMn 2 O 4 。
Preferably, the stirring and dispersing in the first to third steps are carried out for 30min by magnetic stirring and dispersing.
Compared with the prior art, the invention has the following beneficial effects:
1. manganese acetate, lithium acetate, a dispersing agent polyethylene glycol-200, an anionic Gemini surfactant sodium dodecyl diphenyl ether disulfonate and a precipitator ammonium oxalate are selected to perform hydrothermal reaction to obtain a lithium manganate precursor, and then the lithium manganate precursor is placed in a program temperature control box type electric furnace, preheated at 600 ℃ for 6 hours and baked at 900 ℃ for 12 hours to obtain the multi-stage porous single-crystal LiMn 2 O 4 。
2. The lithium ion battery anode material is assembled, and the specific capacity, the multiplying power performance and the cycle performance of the battery are greatly improved.
3. The preparation process has the advantages of rich raw materials, low price, simple operation, no generation of toxic and harmful gas and good application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic illustration of a multi-stage porous single-crystallized micron-sized LiMn for a lithium ion battery anode material of the present invention 2 O 4 X-ray diffraction pattern (XRD);
FIG. 2 is a multi-stage porous single-crystallized micro-scale LiMn of the present invention 2 O 4 Scanning Electron Microscope (SEM) photographs of (a);
FIG. 3 is a schematic diagram of the preparation of LiMn according to the present invention 2 O 4 A first charge-discharge curve of a material-assembled battery;
FIG. 4 is a schematic diagram of the preparation of LiMn according to the present invention 2 O 4 100 cycle stability profile for a material assembled cell.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Multistage porous monocrystalline micron-sized LiMn 2 O 4 The preparation method of the positive electrode material comprises the following steps:
step 1, weighing 0.3676g (1.5 mmol) of manganese acetate tetrahydrate and 0.3061g (3 mmol) of lithium acetate dihydrate, and magnetically stirring and dispersing in 50mL of deionized water to form a uniform solution;
step 2, weighing 0.01g (0.1 mmol) of polyethylene glycol-200 and 0.052g (0.1 mmol) of sodium dodecyl diphenyl ether disulfonate, adding the uniform solution obtained in the step 1, and continuing to magnetically stir and disperse to form a uniform solution;
step 3, weighing 0.8527g (6 mmol) of ammonium oxalate monohydrate, and magnetically stirring and dispersing the ammonium oxalate monohydrate in 30mL of deionized water to form a uniform solution;
step 4, slowly adding 30mL of the ammonium oxalate aqueous solution obtained in the step 3 into the uniform solution obtained in the step 2 to form a mixed solution;
transferring the mixed solution obtained in the step (4) to a stainless steel reaction kettle of a polytetrafluoroethylene liner, sealing, placing in a program-controlled temperature box type electric furnace, starting from room temperature, quickly heating to 200 ℃ at a heating rate of 50 ℃/min, preserving heat for 6 hours, taking out, placing in ice water, quickly cooling to room temperature, taking out the liner, pouring out supernatant, transferring into a centrifuge tube with deionized water, centrifugally separating, and repeatedly washing three times with deionized water and absolute ethyl alcohol respectively to obtain a precursor of synthesized lithium manganate;
and 6, placing the lithium manganate precursor obtained in the step 5 into a quartz boat, and placing the quartz boat into a program temperature control box type electric furnace. In the air atmosphere, heating the resistance furnace at 5 ℃/min, preheating for 6 hours at 600 ℃, then heating at 3 ℃/min, continuously heating to 900 ℃ for roasting for 12 hours, and naturally cooling to obtain the multi-stage porous monocrystalline micron-sized LiMn 2 O 4 。
Preparation of a positive plate: n-methyl-2-pyrrolidone (NMP) is used as a dispersing agent, polyvinylidene fluoride (PVDF) is used as a binder, and acetylene black is used as a conductive agent. Firstly, respectively weighing the prepared LiMn according to the mass ratio of 80:10:10 2 O 4 And (3) placing the anode active material, PVDF and acetylene black in an agate mortar for uniform mixing, adding a proper amount of NMP for wet grinding and dispersing, uniformly coating the mixture on a guide body aluminum foil by using a scraper after uniform dispersion, and drying the mixture in a vacuum drying oven at 100 ℃ to obtain the pole piece. Finally, punching by using a punch to obtain the positive plate with the diameter of 14 mm.
Assembling a battery: liPF with lithium manganate positive electrode material as positive electrode and metal lithium sheet as negative electrode, 1mol/L 6 And (3) dissolving ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate in a volume ratio of 1:1:1 as electrolyte, taking a porous polypropylene film as a diaphragm, assembling and injecting liquid in a glove box filled with high-purity Ar of protective gas, and finally sealing by a sealing machine to assemble the CR2016 type button cell.
And (3) testing charge and discharge performance: the voltage range is 3.0-4.3V, and the current density corresponding to the 1C multiplying power of lithium manganate in the setting process is 148 mA.g -1 。
FIG. 1 is the present inventionMulti-stage porous single-crystallization micron-sized LiMn for positive electrode material of lithium ion battery 2 O 4 As can be seen from FIG. 1, the position of the peak of the X-ray diffraction pattern (XRD) of (C) corresponds to JCPDS 88-0589, and the prepared material is LiMn 2 O 4 And no impurity peak, indicating a pure phase, no impurity.
FIG. 2 is a multi-stage porous single-crystallized micro-scale LiMn of the present invention 2 O 4 As can be seen from fig. 2, the whole is composed of particles of uneven size, and the particles form a multi-stage porous morphology with a size of 2-5 μm. The grain boundary is clear and the crystallinity is good.
FIG. 3 is a schematic diagram of the preparation of LiMn according to the present invention 2 O 4 First charge-discharge curve of a material assembled battery. As can be seen from FIG. 3, the first charge capacity is 125.1mAh g -1 The initial discharge capacity was 118.1mAhg -1 The initial coulomb efficiency reaches more than 95%, which indicates that the material has good electrochemical reversibility.
FIG. 4 is a schematic diagram of the preparation of LiMn according to the present invention 2 O 4 100 cycle stability profile for a material assembled cell. As can be seen from fig. 4, the cycle stability was good, and the capacity retention rate was 90% or more after 100 cycles.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (3)
1. Multistage porous monocrystalline micron-sized LiMn 2 O 4 The preparation method of the positive electrode material is characterized by comprising the following steps:
adding manganese salt and lithium salt into deionized water, and stirring and dispersing uniformly to obtain a mixed solution A; the manganese salt is manganese acetate tetrahydrate; the lithium salt is lithium acetate dihydrate; the molar ratio of the manganese salt to the lithium salt is 1:2;
step two, adding polyethylene glycol and sodium dodecyl diphenyl ether disulfonate into the mixed solution A, and stirring and dispersing uniformly to obtain a mixed solution B; the molar ratio of the polyethylene glycol to the sodium dodecyl diphenyl ether disulfonate to the manganese salt is 1:1:15;
adding ammonium salt into deionized water, and stirring and dispersing uniformly to obtain a mixed solution C;
step four, adding the mixed solution C into the mixed solution B to obtain a mixed solution D;
transferring the mixed solution D into a polytetrafluoroethylene lining reaction kettle, performing hydrothermal reaction, cooling to room temperature after finishing, removing supernatant, and performing centrifugal separation and washing to obtain a precursor of lithium manganate;
step six, roasting the precursor of lithium manganate, and cooling to room temperature after the roasting is finished to obtain the LiMn 2 O 4 A positive electrode material;
in the third step, the ammonium salt is ammonium oxalate; the molar ratio of the ammonium salt to the manganese salt is 4:1; the volume ratio of the ammonium salt to the deionized water is 1:5;
the hydrothermal reaction in the fifth step specifically comprises: in a program temperature control box type electric furnace, starting from room temperature, quickly heating to 200 ℃ at a heating rate of 50 ℃/min, preserving heat for 6 hours, taking out, putting into ice water, and quickly cooling to room temperature;
the roasting in the sixth step specifically comprises the following steps: in a program temperature control box type electric furnace, in an air atmosphere, heating the resistance furnace to 600 ℃ at a speed of 5 ℃/min, preheating for 6 hours, and then continuously heating to 900 ℃ at a speed of 3 ℃/min, and roasting for 12 hours.
2. A multi-stage porous single-crystalline micron-sized LiMn according to claim 1 2 O 4 The preparation method of the positive electrode material is characterized in that the volume ratio of the manganese salt to the deionized water in the first step is 1.5:50.
3. A multi-stage porous single-crystalline micron-sized LiMn according to claim 2 2 O 4 The preparation method of the positive electrode material is characterized in that the polyethylene glycol in the second step is polyethylene glycol-200.
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