CN116477665A - Lithium manganate positive electrode material, preparation method thereof and lithium ion battery - Google Patents
Lithium manganate positive electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN116477665A CN116477665A CN202210051637.8A CN202210051637A CN116477665A CN 116477665 A CN116477665 A CN 116477665A CN 202210051637 A CN202210051637 A CN 202210051637A CN 116477665 A CN116477665 A CN 116477665A
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- lithium manganate
- lithium
- positive electrode
- electrode material
- niobium
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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 91
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000011164 primary particle Substances 0.000 claims abstract description 37
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 28
- 239000010955 niobium Substances 0.000 claims abstract description 28
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011163 secondary particle Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 241000270708 Testudinidae Species 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000010406 cathode material Substances 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910013641 LiNbO 3 Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims 1
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- PYPDMIQMPWEFHX-UHFFFAOYSA-N [Pb].[Co] Chemical compound [Pb].[Co] PYPDMIQMPWEFHX-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical class O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000008719 thickening Effects 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium manganate positive electrode material, a preparation method thereof and a lithium ion battery. The lithium manganate positive electrode material comprises primary particles, wherein the primary particles are stacked to form tortoise-shell-shaped secondary particles through the bonding action of a niobium-containing compound on the surface of the primary particles; wherein the primary particles are monocrystalline particles; the primary particles comprise at least one of spherical, ellipsoidal, or spheroid-like polyhedrons. Experiments show that the specific surface area of the lithium manganate positive electrode material is lower than that of the traditional lithium manganate, the tap density is higher than that of the traditional lithium manganate, and the normal-temperature and high-temperature cycle performance of the lithium manganate positive electrode material is also superior to that of the traditional lithium manganate positive electrode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium manganate positive electrode material, a preparation method thereof and a lithium ion battery.
Background
As a secondary battery having excellent performance, a lithium ion battery has advantages of high energy density and long cycle life, and has been widely used in power and 3C fields. The performance of lithium ion batteries is critically dependent on the performance of the positive electrode materials, and the currently mainstream positive electrode materials comprise lithium cobaltate, lithium iron phosphate, nickel cobalt manganese ternary materials and the like. The ternary material of lithium cobaltate and nickel cobalt manganese has the advantages of high energy density and high tap density, but has poor safety performance. In addition, the lower reserves of cobalt lead to both being expensive. Although the lithium iron phosphate has the advantages of long cycle life and good safety performance, the tap density and the electronic conductivity of the lithium iron phosphate are low, so that the volume energy density and the multiplying power performance of the single battery are limited. In contrast, lithium manganate is low in price and environment-friendly, has the advantages of high voltage, overcharge resistance and high safety performance, and is particularly suitable for the fields of electronic products and small-sized electric tools.
The main problems of the current lithium manganate positive electrode material are poor high-temperature cycle performance, and in addition, lattice distortion and Mn caused by Jahn-Teller effect 4+ In addition to electrolyte decomposition due to the high oxidizing property of (2), a large part of the reasons are derived from Mn 2+ Is dissolved in: liPF in electrolyte 6 React with trace moisture to produce HF, cause disproportionation reaction, mn 2+ The dissolution of (c) will cause both the spinel structure of lithium manganate and the destruction of the negative electrode surface solid electrolyte membrane (SEI), thus causing rapid capacity decay. The current adopted countermeasures mainly comprise surface coating and electrolyte component optimization: for example, patent document CN102569807a discloses a coating modified lithium manganate positive electrode material and a preparation method thereof, wherein a layer of oxides or silicates, phosphates and selenates of metals such as Mg, ti, V are coated on the surface of doped lithium manganate. The patent document with publication number of CN103985903A also discloses an electrolyte for improving the high-temperature performance of the lithium manganate power battery and the lithium manganate power battery, wherein a film forming additive with a synergistic effect, a high-temperature additive, a surfactant and a stabilizer are added into the electrolyte. Although the above scheme can suppress Mn to some extent 2+ The dissolution, however, both the coating process and the additives add to the production steps and costs, which somewhat impair the cost advantage of lithium manganate. In addition, the ionic and electronic conductivities of the coating layers used are low, and the introduction of the additives can also cause thickening of the solid electrolyte membrane (CEI) on the surface of the positive electrode, so that the polarization is increased and the rate performance is reduced by both methods.
Besides surface coating and electrolyte component optimization, research has also been conducted to consider that manganese dissolution can be inhibited from the viewpoint of reducing the specific surface area by regulating and controlling the morphology of lithium manganate. For example, patent document CN103985903a discloses a spherical lithium manganate positive electrode material prepared by doping Ni, mg, fe and other elements, so as to reduce the specific surface area of the conventional lithium manganate positive electrode material. However, the spheroid lithium manganate is a primary particle which is loosely piled up, and has a small particle diameter, so that the reduction of the specific surface area is limited.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a lithium manganate positive electrode material, a preparation method thereof and a lithium ion battery. The lithium manganate anode material has the advantage of small specific surface area and can inhibit Mn 2+ And the dissolution improves the circulation stability, in particular to the high-temperature circulation stability.
In a first aspect, the lithium manganate positive electrode material provided by the invention comprises primary particles, wherein the primary particles are stacked to form secondary particles through the bonding action of niobium-containing compounds on the surfaces of the primary particles;
wherein the primary particles are monocrystalline particles, and the primary particles are at least one of spherical, ellipsoidal or spheroid polyhedrons.
In the present invention, the spheroid polyhedron refers to: spherical or ellipsoidal polyhedrons without distinct edges and corners.
The lithium manganate positive electrode material has unique morphology, single crystal primary particles without obvious edges and corners are piled into secondary particles through the binding action of niobium-containing compounds on the surfaces, and the effect of close packing can be achieved, so that the close packed secondary particles are obtained. Compared with the traditional lithium manganate, the shape of the lithium manganate anode material can greatly reduce the specific surface area, reduce the contact area with electrolyte and inhibit Mn while improving the processing performance 2+ And the dissolution improves the cycle performance, in particular to the high-temperature cycle performance. In addition, the tap density of the lithium manganate anode material is greatly improved compared with that of the traditional lithium manganate, so that the lithium manganate anode material can be increasedThe volumetric energy density of the cell is added.
The following preferred technical solutions are used as the present invention, but not as limitations on the technical solutions provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solutions.
Preferably, the appearance of the secondary particles is tortoise shell-shaped. The tortoise shell shape refers to: after the spherical, ellipsoidal or spheroidic polyhedral primary particles are closely stacked, the surfaces of the polyhedral primary particles are polygonal or curved-sided due to mutual extrusion, so that the surfaces of the secondary particles are tortoise shell-shaped.
The tortoise shell shape refers to the appearance of secondary particles, and the interior of the secondary particles is also a solid structure which is closely packed and is not a hollow structure.
Preferably, the primary particles have a particle size of 1 μm to 10 μm, for example 1 μm, 3 μm, 5 μm, 8 μm, 9 μm or 10 μm, etc.; the secondary particles have a particle diameter of 5 μm to 30 μm, for example, 5 μm, 8 μm, 9 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22.5 μm, 25 μm, 27 μm or 30 μm, etc.
In the present invention, if the primary particles are spherical, the particle diameter is the diameter of the sphere; if the particle size is ellipsoidal, the particle size is the diameter of the long side of the ellipsoid; in the case of a spheroid polyhedron, the particle size is the distance between the furthest two points of the polyhedron.
In the present invention, the particle size of the secondary particles refers to the distance between the two farthest points in the secondary particles.
Preferably, the specific surface area of the lithium manganate positive electrode material is less than 0.5m 2 /g, e.g. 0.5m 2 /g、0.4m 2 /g or 0.3m 2 /g, etc.
Preferably, the surface of the lithium manganate positive electrode material contains a niobium-containing compound partially or entirely. The surface of the lithium manganate positive electrode material may refer to the surface of primary particles and/or the surface of secondary particles. Niobium-containing compound on surface of lithium manganate positive electrode material as coating material can be used for Mn 2+ The dissolution plays a further inhibition role, so that the high-temperature cycle stability of the lithium manganate anode material is greatly improved.
Preferably, the niobium-containing compound is Nb 2 O 5 、LiNbO 3 、Li 3 NbO 4 、LiNbO 2 、LiNb 3 O 8 、Li 7 NbO 6 、NbM x O y And LiNb x M y O z At least one of them. Wherein M is a doping element of lithium manganate, and the doping element M comprises at least one of Al, co, cr, cu, mg, mo, ni, sn, V, W, fe, zn, zr, in, ti, B, la, ce, lu, Y, er and Nb.
Preferably, lithium manganate in the lithium manganate positive electrode material has the following chemical formula: li (Li) x Mn 2-y M y O 4 Wherein x is more than or equal to 0.9 and less than or equal to 1.2, and y is more than or equal to 0 and less than or equal to 1.0.
In the technical scheme, x is more than or equal to 0.9 and less than or equal to 1.2, and x can be, for example, 0.9, 0.95, 1.0, 1.05, 1.1 or 1.2 and the like; y is 0.ltoreq.y.ltoreq.1.0, y may be, for example, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 or the like, and when y takes 0, it means that lithium manganate is undoped, and when y takes a value other than 0, it means that lithium manganate is doped with an M element.
In a second aspect, the preparation method of the lithium manganate positive electrode material provided by the invention comprises the following specific steps:
and mixing a lithium source compound, a manganese source compound and a niobium source compound or the three compounds with a doped metal element compound to obtain a precursor. Sintering the precursor in an oxidizing atmosphere, and adjusting preparation parameters to enable primary particles of lithium manganate to be mutually extruded in the growth process, and forming tortoise shell-shaped secondary particles through the bonding effect of niobium-containing compounds on the surfaces of the primary particles;
wherein the preparation parameters include sintering temperature and heating rate.
In the method of the present invention, the rate of temperature increase means a rate of temperature increase to the sintering temperature.
In the method of the invention, the preparation parameters refer to various process parameters in the process of preparing the lithium manganate positive electrode material, such as sintering temperature, sintering time, heating rate, adding amount of niobium source compound and precursorMixing time. According to the method, the niobium-containing compound is added into the precursor, so that the surface energy distribution of the lithium manganate is homogenized in the sintering process, the (111) plane proportion is reduced, the crystal face index is increased, primary particles (such as spheres, ellipsoids or spheroidoid polyhedrons) without obvious edges and angles are obtained, the primary particles of the lithium manganate can be mutually extruded in the growth process by adjusting preparation parameters (such as adjusting the sintering temperature and the heating rate), and the primary particles which are mutually extruded are bonded through the niobium-containing compound generated on the surfaces of the primary particles, so that the tortoise shell-shaped secondary particles with the primary particles tightly stacked are enabled, the specific surface area of the lithium manganate is effectively reduced, and meanwhile, the tap density of the lithium manganate can be improved. In addition, the niobium-containing coating on the surface of the lithium manganate can resist Mn 2+ The dissolution plays a further inhibition role, so that the high-temperature cycle stability of the lithium manganate anode material is greatly improved.
Preferably, the lithium source compound includes at least one of lithium carbonate, lithium hydroxide, lithium oxalate, lithium nitrate and lithium oxalate, but is not limited to the above-listed species, and other lithium source compounds commonly used in the art are equally applicable to the present invention.
Preferably, the manganese source compound includes at least one of manganese hydroxide, manganese dioxide, manganomanganic oxide, manganese oxalate, electrolytic manganese dioxide and manganese carbonate, but is not limited to the above-listed species, and other manganese source compounds commonly used in the art are equally applicable to the present invention.
Preferably, the niobium source compound comprises niobium oxalate and/or niobium pentoxide.
Preferably, the mass ratio of the niobium source compound in the precursor is 0.05% -5%, for example 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.3%, 1.5%, 1.7%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.7%, 4%, 4.2%, 4.3%, 4.5%, 4.7% or 5%, etc.
In the invention, the addition of the niobium source compound can adjust the surface energy of lithium manganate on one hand and form the niobium-containing compound on the surfaces of the primary particles and/or the secondary particles on the other hand, thereby playing a role of bonding and/or coating.
In an alternative embodiment, the addition of the niobium source compound may effect doping of the lithium manganate.
Preferably, the raw materials adopted by the mixing further comprise a doping element M source compound, and the doping element M source compound comprises at least one of an oxide, a hydroxide, a carbonate, a nitrate and an oxalate of the doping element M.
Preferably, the method of mixing includes any one of spray granulation, mechanical agitation or ball milling.
As a preferred embodiment of the method of the present invention, the oxidizing atmosphere includes an oxygen atmosphere or an air atmosphere.
Preferably, the rate of temperature rise is 2℃to 15℃such as 2℃3℃4℃5℃6℃7℃8℃9℃10℃11℃12℃13℃14℃15℃etc.
Preferably, the sintering temperature is 600 ℃ to 1200 ℃, for example 600 ℃, 625 ℃, 650 ℃, 675 ℃, 700 ℃, 730 ℃, 760 ℃, 800 ℃, 835 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, or the like.
Preferably, the sintering time is 5h-48h, such as 5h, 6h, 8h, 10h, 12h, 14h, 15h, 18h, 20h, 24h, 28h, 30h, 35h, 38h, 40h, 42h, 45h, 48h, or the like. The sintering time is the heat preservation time after the temperature reaches the sintering temperature.
In a third aspect, the present invention provides a lithium ion battery comprising the lithium manganate cathode material of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a lithium manganate positive electrode material with a unique tortoise-shell shape, wherein monocrystal primary particles without obvious edges and corners are closely packed into tortoiseshell-shaped secondary particles.
Experiments show that the specific surface area of the lithium manganate anode material is lower than that of the traditional lithium manganate, and the specific surface area is 0.8m 2 A/g or less; high tap densityIn the traditional lithium manganate, the tap density is 1.9g/cm 3 The above; the normal temperature (25 ℃) and high temperature (60 ℃) cycle performance of the assembled lithium manganate/metal lithium half battery is also superior to that of the traditional lithium manganate positive electrode material, and after normal temperature cycle and high temperature cycle at 1C multiplying power, the capacity retention rate is respectively more than 85% and 65%.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of lithium manganate prepared in example 1.
A and b in fig. 2 are Scanning Electron Microscope (SEM) images of the lithium manganate prepared in example 1 at different magnifications.
Fig. 3 is a normal temperature 1C first-turn charge-discharge curve of lithium manganate prepared in example 1.
Fig. 4 is an SEM image of lithium manganate prepared in comparative example 1.
FIG. 5 is a 1C ordinary temperature (25 ℃) cycle life curve of lithium manganate prepared in example 1 and comparative example 1.
FIG. 6 is a graph showing the cycle life at 1C at high temperature (60 ℃) of lithium manganate prepared in example 1 and comparative example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In the embodiment of the invention, the normal temperature is 25 ℃, and the high temperature is 60 ℃.
Example 1
Lithium carbonate, manganese hydroxide and niobium oxalate are used as precursors, wherein the lithium carbonate and the manganese hydroxide are prepared according to the atomic composition ratio Li of the product 1.05 Mn 2 O 4 And mixing, wherein the mass ratio of niobium oxalate in the whole precursor is 3%. And mixing the precursors by adopting dry ball milling, wherein the ball-material ratio is 1:5, the rotating speed is 150 rmp, and the ball milling time is 120 min. And placing the mixed precursor in an oxygen atmosphere, heating to 1000 ℃ at a heating rate of 8 ℃/min, and preserving heat for 24 hours to obtain a target product. As can be seen from the XRD pattern of fig. 1, the prepared lithium manganate cathode material has a spinel structure.
Example 2
The difference from example 1 is that the niobium source compound in the precursor is niobium pentoxide.
Example 3
The difference from example 1 is that the precursor is lithium carbonate, manganese hydroxide, aluminum hydroxide, and niobium oxalate in terms of the atomic composition ratio Li of the product 1.05 Mn 1.95 Al 0.05 O 4 The mass ratio of niobium oxalate in the whole precursor was the same as in example 1 (3%).
Example 4
The difference from example 1 is that the mass ratio of niobium oxalate in step (1) in the entire precursor is 5%.
Example 5
The difference from example 1 is that the precursor mixing mode of step (1) is wet ball milling, the adopted grinding aid is absolute ethyl alcohol, the mass ratio of the grinding aid to the precursor is 3:10, the ball-material ratio is 1:5, the rotating speed is 150 rmp, and the ball milling time is 120 min.
Example 6
The difference from example 1 is that the sintering temperature in step (2) was 800 ℃, the temperature rising rate was 9 ℃/min, and the sintering time was 40h.
Comparative example 1
The difference from example 1 is that niobium oxalate was not contained in the precursor of comparative example 1.
And (3) testing:
1. specific surface area test
The specific surface area test is carried out by adopting a full-automatic specific surface area and a micropore analyzer and is obtained through an adsorption and desorption curve of nitrogen. The results are shown in Table 1.
2. Tap density test
The tap density test adopts the general test method of tap density of powder products, national standard number: GB/T21354-2008/ISO 3953:1993. Lithium manganate is filled in a 100ml measuring cylinder, the stroke distance is 3mm, the vibration frequency is 200 times/min, and the lithium manganate passes through rho t Obtained =m/v. Wherein: ρ t And the tap density is represented by m, the mass of lithium manganate, and the volume of lithium manganate after tap is represented by v. The results are shown inTable 1.
3. Electrochemical performance testing at moderate and high temperatures
The lithium manganate/metal lithium button half battery is assembled, the mass ratio of lithium manganate, a conductive agent (Super-P) and a binder (PVDF) in a positive plate is 18:1:1, and an electrolyte is LB303 (1M LiPF) 6 ， EC:DEC:EMC=1:1:1 Vol）。
(1) First-turn capacity test
Charging and discharging at 1C rate in 25 ℃. The results are shown in Table 1.
(2) Cycle capacity retention test
Cycling at 1C rate in a 25 ℃ environment. The results are shown in Table 1.
TABLE 1 specific surface area and tap Density for inventive examples 1-5 and comparative example 1
。
It can be seen from the specific surface areas and tap densities of examples 1 to 6 and comparative example 1 that the specific surface areas and tap densities of comparative example 1 are greatly reduced as compared with examples 1 to 6, and the tap densities are remarkably improved. Meanwhile, with the increase of the doping amount of niobium, the specific surface area of the lithium manganate positive electrode material is further reduced, and the tap density is further improved. FIG. 2 is a SEM image of example 1, which shows that the primary particles are spheroid, the primary particles have a particle size of 2 μm to 6 μm and the secondary particles have a particle size of about 5 μm to 25. Mu.m. Fig. 4 is an SEM image of comparative example 1, whose primary particle size is in a remarkable octahedral morphology.
TABLE 2 electrochemical Properties of examples 1-6 and comparative example 1 of the present invention
。
As can be seen from the electrochemical performances of examples 1-6 and comparative example 1, the normal temperature and high temperature cycle stability of examples 1-6 is improved compared with comparative example 1 after niobium doping and morphology regulation. FIG. 3 shows the 1C first-turn charge-discharge curve of the sample of example 1, with a specific first-turn discharge capacity of 110.0 mAh/g. As shown in FIGS. 5 and 6, the sample of example 1 had a capacity retention of 90.9% and 72.6% at normal temperature (25 ℃) and high temperature (60 ℃) after 500 cycles at 1C. And after 500 circles of 1C, the capacity retention rates of the lithium manganate positive electrode material of the comparative example 1 are only 81.6% and 43.9% respectively in normal temperature and high temperature cycles, wherein the attenuation of the lithium manganate positive electrode material is increased after 400 circles of normal temperature cycles, and the attenuation of the lithium manganate positive electrode material is increased after 320 circles of high temperature cycles.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (10)
1. The lithium manganate positive electrode material is characterized by comprising primary particles, wherein the primary particles are piled up to form secondary particles through the bonding effect of niobium-containing compounds on the surfaces of the primary particles;
wherein the primary particles are monocrystalline particles, and the primary particles comprise at least one of spherical, ellipsoidal or spheroid-like polyhedrons.
2. The lithium manganate positive electrode material according to claim 1, wherein the appearance of the secondary particles is tortoise shell-like; the particle size of the primary particles is 1-10 mu m, and the particle size of the secondary particles is 5-30 mu m; the specific surface area of the lithium manganate positive electrode material is less than 0.8m 2 /g; the surface of the lithium manganate positive electrode material contains a niobium-containing compound partially or completely.
3. The lithium manganate positive electrode material according to claim 2, wherein the niobium-containing compound is selected from Nb 2 O 5 、LiNbO 3 、Li 3 NbO 4 、LiNbO 2 、LiNb 3 O 8 、Li 7 NbO 6 、NbM x O y And LiNb x M y O z At least one of (a) and (b); wherein M is a doping element of lithium manganate, and the doping elementM is at least one of Al, co, cr, cu, mg, mo, ni, sn, V, W, fe, zn, zr, in, ti, B, la, ce, lu, Y, er and Nb.
4. The lithium manganate cathode material according to claim 3, wherein the mass ratio of the niobium element in the lithium manganate cathode material is 0.05-5%.
5. The lithium manganate positive electrode material according to claim 4, wherein the lithium manganate in the lithium manganate positive electrode material has the following chemical formula: li (Li) x Mn 2-y M y O 4 Wherein x is more than or equal to 0.9 and less than or equal to 1.2, and y is more than or equal to 0 and less than or equal to 1.0, and M is the doping element of claim 4.
6. A method for preparing a lithium manganate positive electrode material according to any one of claims 1-5, characterized by the specific steps of:
mixing a lithium source compound, a manganese source compound and a niobium source compound, or mixing the three compounds with a doped metal compound to obtain a precursor; sintering the precursor in an oxidizing atmosphere, and adjusting preparation parameters to enable primary particles of lithium manganate to be mutually extruded in the growth process, and forming tortoise shell-shaped secondary particles through the bonding effect of niobium-containing compounds on the surfaces of the primary particles;
the preparation parameters comprise sintering temperature and heating rate, wherein the heating rate is 2-15 ℃; the sintering temperature is 600-1200 ℃, and the sintering time is 5-48 h.
7. The method of manufacturing according to claim 6, wherein:
the lithium source compound is at least one selected from lithium carbonate, lithium hydroxide, lithium oxalate, lithium nitrate and lithium oxalate;
the manganese source compound is selected from at least one of manganese hydroxide, manganese dioxide, manganous oxide, manganese oxalate, electrolytic manganese dioxide and manganese carbonate;
the niobium source compound comprises niobium oxalate and/or niobium pentoxide;
the mass ratio of the niobium element in the lithium manganate positive electrode material is 0.05-5%;
the raw materials adopted by the mixing also comprise a doping element M source compound, wherein the doping element M source compound is at least one of oxide, hydroxide, carbonate, nitrate and oxalate of the doping element M.
8. The method of preparation according to claim 6 or 7, wherein the method of mixing comprises any one of spray granulation, mechanical stirring or ball milling.
9. The method according to claim 8, wherein the oxidizing atmosphere is an oxygen atmosphere or an air atmosphere.
10. A lithium ion battery comprising the lithium manganate positive electrode material of any one of claims 1-6.
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