CN115411261A - Nano single crystal type lithium-rich manganese-based positive electrode material and preparation method and application thereof - Google Patents
Nano single crystal type lithium-rich manganese-based positive electrode material and preparation method and application thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 80
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000013078 crystal Substances 0.000 title claims abstract description 49
- 239000007774 positive electrode material Substances 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000010406 cathode material Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 48
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- 239000002250 absorbent Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 6
- 239000011358 absorbing material Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 125000000271 carboxylic acid salt group Chemical group 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000002759 woven fabric Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 description 39
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 16
- 239000002245 particle Substances 0.000 description 13
- 230000002745 absorbent Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 9
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 8
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride 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
- 230000003446 memory effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 nano single crystal type lithium-rich manganese-based anode material and a preparation method and application thereof, wherein the chemical formula of the nano single crystal type lithium-rich manganese-based anode material is as follows: li (1+x) Mn y Sn z M k O 2 Wherein 0 is<x≤0.5，0.5≤y<1，0<z<0.5，0<k<0.2, M is at least one of metal elements of Ti, co, W, ni, nb. The nano single crystal type lithium-rich manganese-based cathode material has excellent cycle performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a nano single crystal type lithium-rich manganese-based anode material as well as a preparation method and application thereof.
Background
Since the lithium ion battery was successfully produced commercially at the end of the last century, the lithium ion battery has been more and more widely used due to its advantages of high specific capacity, good cycle performance, no memory effect, etc. Particularly, in recent years, with the rapid development of new energy automobiles, the demand for lithium ion batteries is increasing, and meanwhile, higher requirements are put forward on the performance of the lithium ion batteries.
At present, two mainstream power batteries applied to new energy automobiles are available, one is a lithium iron phosphate type lithium ion battery with the energy density of 150-180 Wh/kg, and the lithium iron phosphate type lithium ion battery has lower energy density, good safety performance and lower cost. The other is a ternary lithium ion battery with the energy density of about 200-250 Wh/kg, which has better capacity and cycle performance but higher cost. Even if a ternary lithium ion battery with high energy density is loaded, the endurance mileage of a mainstream pure electric vehicle in the market is mostly about 400-600 km, and people still have mileage anxiety for the pure electric vehicle due to the problems of imperfect charging facilities, low charging speed and the like. In order to improve the energy density of the battery and increase the endurance mileage of the pure electric vehicle, new battery materials and structural systems need to be developed.
The lithium-rich manganese-based positive electrode material has high specific capacity of 250mAh/g, low content of expensive rare metals and relatively low cost. It is considered to be one of the most potential next generation lithium ion battery materials. But has poor cycling performance due to severe voltage decay and irreversible anion redox reaction during the cycling process.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a nano single crystal type lithium-rich manganese-based cathode material as well as a preparation method and application thereof.
The technical purpose of the invention is realized by the following technical scheme:
a nano single crystal type lithium-rich manganese-based cathode material has a chemical formula as follows: li (1+x) Mn y Sn z M k O 2 Wherein 0 is<x≤0.5，0.5≤y<1，0<z<0.5，0<k<0.2, M is at least one of metal elements of Ti, co, W, ni, nb.
Preferably, in the chemical formula, x is more than or equal to 0.1 and less than or equal to 0.3, y is more than or equal to 0.55 and less than or equal to 0.7, and z is more than or equal to 0.1 and less than or equal to 0.3.
Preferably, the chemical formula is Li 1.15 Mn 0.58 Sn 0.15 Co 0.07 O 2 、Li 1.21 Mn 0.55 Sn 0.20 Ti 0.02 O 2 、Li 1.18 Mn 0.60 Sn 0.12 Nb 0.05 O 2 And Li 1.20 Mn 0.58 Sn 0.15 Ni 0.06 O 2 At least one of (1).
Preferably, the particle size of the nano single crystal type lithium-rich manganese-based cathode material is 100-1000nm.
The preparation method of the nano single crystal type lithium-rich manganese-based cathode material comprises the following steps:
(1) Dissolving soluble Li salt, soluble Mn salt, soluble Sn salt and soluble M salt in water to form solution A;
(2) Adding an ammonia water solution into the solution A, and adjusting the pH value to be alkaline to form a solution B;
(3) Adding a water absorbing material into the solution B, absorbing the solution B by the water absorbing material to form a swelling material, and drying the swelling material to obtain a precursor material containing Li, mn, sn and M metals;
(4) And sintering the precursor material, preserving heat and crushing to obtain the nano single crystal type lithium-rich manganese-based anode material.
Preferably, the soluble Li salt in step (1) is at least one of lithium nitrate, lithium hydroxide or lithium acetate.
Preferably, the soluble Mn salt in step (1) is at least one of manganese nitrate, manganese sulfate, manganese chloride or manganese acetate.
Preferably, the soluble Sn salt in step (1) is at least one of tin tetrachloride, stannous chloride or stannous sulfate.
Preferably, the soluble M salt in step (1) is at least one of titanium tetrachloride, butyl titanate, titanium nitrate, cobalt sulfate, cobalt chloride, ammonium paratungstate, tungsten trioxide, nickel sulfate, nickel nitrate, niobium nitrate or niobium pentachloride.
Preferably, the total metal concentration of the solution A in the step (1) is less than or equal to 1mol/L.
Preferably, in the step (2), the pH is adjusted to be alkaline, namely, the pH is adjusted to 7.0-9.0.
Further preferably, in the step (2), the pH is adjusted to be alkaline, that is, the pH is adjusted to 7.0 to 8.0.
Preferably, in the step (3), the water absorbent material is a water absorbent resin material containing carboxylic acid groups and/or carboxylic acid salt groups.
Preferably, the water-absorbent resin material is at least one of starch crosslinking water-absorbent resin, polyacrylate water-absorbent resin or vinyl acetate copolymer water-absorbent resin.
Preferably, in the step (3), the drying temperature is 100-200 ℃.
Further preferably, in the step (3), the drying temperature is 120-150 ℃.
Preferably, in the step (3), the sintering temperature is 800-1200 ℃, and the heat preservation time is 8-12h.
Further preferably, in the step (3), the sintering temperature is 900-1000 ℃, and the heat preservation time is 10-12h.
Preferably, in the step (4), the material obtained by sintering, heat preservation and crushing the precursor material is further subjected to sieving treatment.
The nano single crystal type lithium-rich manganese-based cathode material is applied to lithium ion batteries.
The invention has the beneficial effects that:
(1) The nanometer single crystal type lithium-rich manganese-based positive electrode material improves the voltage attenuation problem of the lithium-rich manganese-based material by doping the M element, reduces the initial valence state of Mn by introducing the high-valence state element, and inhibits the occurrence of the irreversible redox reaction of anions, thereby improving the cycle performance of the material;
(2) The nano single crystal lithium-rich manganese-based anode material adopts specific water-absorbent resin as a template agent and a precursor carrier in the preparation method, the specific water-absorbent resin is a polymer containing carboxylic acid groups and carboxylate groups, is generally weakly acidic, and has stronger absorption effect on a weakly alkaline solution.
Drawings
FIG. 1 is an SEM image of a nano-single crystal type lithium-rich manganese-based cathode material in example 1 of the present invention;
FIG. 2 is a charging and discharging curve (0.1C) of the nano single crystal type lithium-rich manganese-based cathode material under the first period of 2.0-4.8V voltage in the embodiment 1 of the invention;
fig. 3 is a schematic diagram of the cycle performance of the nano single crystal type lithium-rich manganese-based positive electrode material of embodiment 1 at 0.33C for 100 cycles after being activated for 2 cycles at 0.1C.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1:
a nano single crystal type lithium-rich manganese-based cathode material has a chemical formula as follows: li 1.15 Mn 0.58 Sn 0.15 Co 0.07 O 2 。
The preparation method of the nano single crystal type lithium-rich manganese-based anode material comprises the following steps:
(1) Weighing 1.15mol of lithium nitrate, 0.58mol of manganese nitrate, 0.15mol of stannous sulfate and 0.07mol of cobalt nitrate, dissolving the lithium nitrate, the manganese nitrate, the stannous sulfate and the cobalt nitrate in 5L of deionized water, and stirring the solution to fully dissolve the lithium nitrate, the manganese nitrate and the cobalt nitrate to form a solution A;
(2) Dropwise adding an ammonia water solution into the solution A while stirring, and adjusting the pH to 8.0 to form a solution B;
(3) Adding 500g of polyacrylic acid super absorbent resin into the solution B, completely absorbing the solution B by the super absorbent resin to form swollen resin particles, and drying the swollen resin particles at 150 ℃ for 10 hours to obtain a precursor material containing Li, mn, sn and Co metals;
(4) Placing the obtained precursor material in a muffle furnace for high-temperature sintering at 900 ℃, keeping the temperature for 10 hours, crushing and sieving the sintered material to obtain the nano single-crystal lithium-rich manganese-based material Li 1.15 Mn 0.58 Sn 0.15 Co 0.07 O 2 。
The shape of the obtained lithium-rich manganese-based material is shown in figure 1 through the detection of a Scanning Electron Microscope (SEM), and the shape of the material is a nano single crystal particle with the particle size of 100-1000nm.
The obtained nano single crystal type lithium-rich manganese-based material Li 1.15 Mn 0.58 Sn 0.15 Co 0.07 O 2 The button cell positive plate is prepared by mixing, coating and tabletting, lithium metal is taken as a negative plate, and a diaphragm and electrolyte are added to prepare the button cell so as to test the electrical property of the button cell. As shown in figure 2, the obtained nano single crystal type lithium-rich manganese-based material Li 1.15 Mn 0.58 Sn 0.25 Co 0.02 O 2 The first-week discharge capacity is 254.4mAh g under the voltage of 2.0-4.8V -1 . As shown in fig. 3, the button cell was activated at 0.1C for 2 cycles, and then the discharge capacity was 216.2mAh g at 0.33C for 100 cycles -1 After the number of activation cycles was removed, the capacity retention rate was 92.2%, exhibiting excellent capacity retention rate.
Example 2:
a nano single crystal type lithium-rich manganese-based cathode material has a chemical formula as follows: li 1.21 Mn 0.55 Sn 0.20 Ti 0.02 O 2 。
The preparation method of the nano single crystal type lithium-rich manganese-based cathode material comprises the following steps:
(1) Weighing 1.21mol of lithium acetate, 0.55mol of manganese nitrate, 0.20mol of stannous sulfate and 0.02mol of titanium tetrachloride, dissolving in 6L of cold deionized water, and stirring to fully dissolve to form a solution A;
(2) Dropwise adding an ammonia water solution into the solution A while stirring, and adjusting the pH to 7.5 to form a solution B;
(3) Adding 550g of vinyl acetate copolymer super absorbent resin into the solution B, completely absorbing the solution B by the super absorbent resin to form swollen resin particles, and drying the swollen resin particles at 150 ℃ for 10 hours to obtain a precursor material containing Li, mn, sn and Ti metals;
(4) Placing the obtained precursor material in a muffle furnace for high-temperature sintering at 950 ℃, keeping the temperature for 10.5 hours, crushing and sieving the sintered material to obtain the nano single crystal type lithium-rich manganese-based material Li 1.21 Mn 0.55 Sn 0.20 Ti 0.02 O 2 。
The obtained nano single crystal type lithium-rich manganese-based material Li 1.21 Mn 0.55 Sn 0.20 Ti 0.02 O 2 The button cell positive plate is prepared by mixing, coating and tabletting, lithium metal is taken as a negative plate, and a diaphragm and electrolyte are added to prepare the button cell so as to test the electrical property of the button cell. Under the voltage of 2.0-4.8V, the first-week discharge capacity is 255.1mAh g -1 . After the button cell is activated for 2 circles at 0.1 ℃, the discharge capacity of the button cell is 213.5mAh g after the button cell is cycled for 100 weeks at 0.33 DEG C -1 After the number of activation turns is removed, the capacity retention rate is 91.6%.
Example 3:
a nano single crystal type lithium-rich manganese-based cathode material has a chemical formula as follows: li 1.18 Mn 0.60 Sn 0.12 Nb 0.05 O 2 。
The preparation method of the nano single crystal type lithium-rich manganese-based anode material comprises the following steps:
(1) Weighing 1.18mol of lithium nitrate, 0.60mol of manganese sulfate, 0.12mol of stannous sulfate and 0.05mol of niobium nitrate, dissolving in 4L of cold deionized water, and stirring to fully dissolve to form a solution A;
(2) Dropwise adding an ammonia water solution into the solution A while stirring, and adjusting the pH to 7.7 to form a solution B;
(3) Adding 450g of starch crosslinking type super absorbent resin into the solution B, completely absorbing the solution B by the super absorbent resin to form swelling resin particles, and drying the swelling resin particles at 150 ℃ for 10 hours to obtain a precursor material containing Li, mn, sn and Nb metals;
(4) Placing the obtained precursor material in a muffle furnace for high-temperature sintering at 950 ℃, keeping the temperature for 10.5 hours, crushing and sieving the sintered material to obtain the nano single crystal type lithium-rich manganese-based material Li 1.18 Mn 0.60 Sn 0.12 Nb 0.05 O 2 。
The obtained nano single crystal type lithium-rich manganese-based material Li 1.18 Mn 0.60 Sn 0.12 Nb 0.05 O 2 The button cell positive plate is prepared by size mixing, coating and tabletting, lithium metal is taken as a negative plate, and a diaphragm and electrolyte are added to prepare the button cell so as to test the electrical property of the button cell. Under the voltage of 2.0-4.8V, the first-week discharge capacity is 248.8mAh g -1 . After the button cell is activated for 2 circles at 0.1 ℃, the discharge capacity of the button cell is 215.5mAh & g after the button cell is cycled for 100 weeks at 0.33 DEG C -1 After the number of activation cycles was removed, the capacity retention rate was 92.6%.
Example 4:
a nano single crystal type lithium-rich manganese-based cathode material has a chemical formula as follows: li 1.20 Mn 0.58 Sn 0.15 Ni 0.06 O 2 。
The preparation method of the nano single crystal type lithium-rich manganese-based cathode material comprises the following steps:
(1) Weighing 1.20mol of lithium hydroxide, 0.58mol of manganese nitrate, 0.15mol of stannous chloride and 0.06mol of nickel nitrate, dissolving in 8L of cold deionized water, and stirring to fully dissolve to form a solution A;
(2) Dropwise adding an ammonia water solution into the solution A while stirring, and adjusting the pH to 8.0 to form a solution B;
(3) Adding 750g of vinyl acetate copolymer super absorbent resin into the solution B, completely absorbing the solution B by the super absorbent resin to form swollen resin particles, and drying the swollen resin particles at 120 ℃ for 12 hours to obtain a precursor material containing Li, mn, sn and Ni metals;
(4) Placing the obtained precursor material in a muffle furnace for high-temperature sintering at 940 ℃, preserving the heat for 12 hours, crushing and sieving the sintered material to obtain the nano single crystalLithium-rich manganese-based material Li 1.20 Mn 0.58 Sn 0.15 Ni 0.06 O 2 。
The obtained nano single crystal type lithium-rich manganese-based material Li 1.20 Mn 0.58 Sn 0.15 Ni 0.06 O 2 The button cell positive plate is prepared by mixing, coating and tabletting, lithium metal is taken as a negative plate, and a diaphragm and electrolyte are added to prepare the button cell so as to test the electrical property of the button cell. Under the voltage of 2.0-4.8V, the first-week discharge capacity is 255.4mAh g -1 . After the button cell is activated for 2 circles at 0.1 ℃, the discharge capacity of the button cell is 218.5mAh g after the button cell is cycled for 100 weeks at 0.33 DEG C -1 After the number of activation turns is removed, the capacity retention rate is 91.2%.
Comparative example 1: (comparative example 1 No cobalt nitrate was added during the preparation)
A preparation method of a nano single crystal type lithium-rich manganese-based positive electrode material comprises the following steps:
(1) Weighing 1.15mol of lithium nitrate, 0.58mol of manganese nitrate and 0.25mol of stannous sulfate, dissolving the lithium nitrate, the manganese nitrate and the stannous sulfate in 5L of deionized water, and stirring the solution to fully dissolve the lithium nitrate, the manganese nitrate and the stannous sulfate to form a solution A;
(2) Dropwise adding an ammonia water solution into the solution A while stirring, and adjusting the pH to 8.0 to form a solution B;
(3) Adding 500g of polyacrylic acid super absorbent resin into the solution B, completely absorbing the solution B by the super absorbent resin to form swollen resin particles, and drying the swollen resin particles at 150 ℃ for 10 hours to obtain a precursor material containing Li, mn, sn and Co metals;
(4) And (3) placing the obtained precursor material in a muffle furnace for high-temperature sintering at 900 ℃, keeping the temperature for 10 hours, and crushing and sieving the sintered material to obtain the nano single-crystal lithium-rich manganese-based material.
The obtained nano single crystal type lithium-rich manganese-based material is prepared into a button cell positive plate by size mixing, coating and tabletting, lithium metal is taken as a negative plate, and a diaphragm and electrolyte are added to prepare the button cell so as to test the electrical property of the button cell. Under the voltage of 2.0-4.8V, the first-week discharge capacity is 250.8 mAh.g -1 . After the button cell is activated for 2 circles at 0.1 ℃, the discharge capacity of the button cell is 100 weeks at 0.33 ℃ in circulation214.3mAh·g -1 And after the number of the activation turns is removed, the capacity retention rate is 82.5%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A nano single crystal type lithium-rich manganese-based cathode material is characterized in that: the chemical formula is as follows: li (1+x) Mn y Sn z M k O 2 Wherein 0 is<x≤0.5，0.5≤y<1，0<z<0.5，0<k<0.2, M is at least one of metal elements of Ti, co, W, ni and Nb.
2. The nano single crystal type lithium-rich manganese-based positive electrode material as claimed in claim 1, wherein: in the chemical formula, x is more than or equal to 0.1 and less than or equal to 0.3, y is more than or equal to 0.55 and less than or equal to 0.7, z is more than or equal to 0.1 and less than or equal to 0.3, and k-woven fabrics of 0 are woven fabrics of 0.2.
3. The nano single crystal type lithium-rich manganese-based positive electrode material as claimed in claim 2, wherein: the chemical formula is Li 1.15 Mn 0.58 Sn 0.15 Co 0.07 O 2 、Li 1.21 Mn 0.55 Sn 0.20 Ti 0.02 O 2 、Li 1.18 Mn 0.60 Sn 0.12 Nb 0.05 O 2 And Li 1.20 Mn 0.58 Sn 0.15 Ni 0.06 O 2 At least one of (1).
4. The nano single crystal type lithium-rich manganese-based positive electrode material as claimed in claim 1, wherein: the grain size of the nano single crystal type lithium-rich manganese-based anode material is 100-1000nm.
5. A method for preparing the nano single crystal type lithium-rich manganese-based cathode material as claimed in any one of claims 1 to 4, wherein the method comprises the following steps: the method comprises the following steps:
(1) Dissolving soluble Li salt, soluble Mn salt, soluble Sn salt and soluble M salt in water to form solution A;
(2) Adding an ammonia water solution into the solution A, and adjusting the pH value to be alkaline to form a solution B;
(3) Adding a water absorbing material into the solution B, absorbing the solution B by the water absorbing material to form a swelling material, and drying the swelling material to obtain a precursor material containing Li, mn, sn and M metals;
(4) And sintering the precursor material, preserving heat and crushing to obtain the nano single crystal type lithium-rich manganese-based anode material.
6. The method for preparing the nano single crystal type lithium-rich manganese-based cathode material according to claim 5, wherein the method comprises the following steps: the total metal concentration of the solution A in the step (1) is less than or equal to 1mol/L.
7. The method for preparing the nano single crystal type lithium-rich manganese-based positive electrode material according to claim 5, wherein the method comprises the following steps: in the step (2), the pH is adjusted to be alkaline, namely the pH is adjusted to be 7.0-9.0.
8. The method for preparing the nano single crystal type lithium-rich manganese-based positive electrode material according to claim 5, wherein the method comprises the following steps: in the step (3), the water-absorbent material is a water-absorbent resin material containing carboxylic acid groups and/or carboxylic acid salt groups.
9. The method for preparing the nano single crystal type lithium-rich manganese-based positive electrode material according to claim 8, wherein the method comprises the following steps: the water-absorbent resin material is at least one of starch crosslinking water-absorbent resin, polyacrylate water-absorbent resin or vinyl acetate copolymer water-absorbent resin.
10. Use of the nano single crystal type lithium-rich manganese-based positive electrode material according to any one of claims 1 to 4 in a lithium ion battery.
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| PCT/CN2022/120354 WO2024036695A1 (en) | 2022-08-18 | 2022-09-21 | Nano single-crystal type lithium-rich manganese-based positive electrode material, and preparation method therefor and use thereof |
| FR2308674A FR3138967A1 (en) | 2022-08-18 | 2023-08-11 | SINGLE CRYSTALLINE CATHODE NANOMATERIAL BASED ON LITHIUM-RICH MANGANESE, AS WELL AS ITS PREPARATION METHOD AND ITS USE |
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