CN113782721A - Double-coated lithium manganate composite material and preparation method thereof - Google Patents
Double-coated lithium manganate composite material and preparation method thereof Download PDFInfo
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- CN113782721A CN113782721A CN202111012944.7A CN202111012944A CN113782721A CN 113782721 A CN113782721 A CN 113782721A CN 202111012944 A CN202111012944 A CN 202111012944A CN 113782721 A CN113782721 A CN 113782721A
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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 72
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 239000011572 manganese Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000012266 salt solution Substances 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000007873 sieving Methods 0.000 claims abstract description 24
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000004927 fusion Effects 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 229910017278 MnxOy Inorganic materials 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 229910015645 LiMn Inorganic materials 0.000 claims abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 229940044175 cobalt sulfate Drugs 0.000 claims description 7
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 229940099596 manganese sulfate Drugs 0.000 claims description 7
- 239000011702 manganese sulphate Substances 0.000 claims description 7
- 235000007079 manganese sulphate Nutrition 0.000 claims description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 3
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 9
- 229910001429 cobalt ion Inorganic materials 0.000 description 9
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 9
- 229910001437 manganese ion Inorganic materials 0.000 description 9
- 229910001453 nickel ion Inorganic materials 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 229940053662 nickel sulfate Drugs 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- 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
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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
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- 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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The application relates to the field of lithium manganate electrode materials, in particular to a double-coated lithium manganate composite material and a preparation method thereof, wherein the preparation method comprises the following steps: adding MnxOyDispersing in pure water, adding ternary precursor metal salt solution, complexing agent and precipitant, heating in protective atmosphere to obtain precipitate, washing and dryingDrying, crushing and sieving to obtain MnxOy@NiaCobMn(1‑a‑b)(OH)2Denoted as Q1; mixing and grinding Q1 and lithium salt, roasting in oxygen or air atmosphere, crushing and sieving after roasting is finished to obtain LiMn2O4@LiNiaCobMn(1‑a‑b)O2Denoted as Q2; mixing Q2 with MdOeCarrying out mechanical fusion to obtain the LiMn of the double-coated lithium manganate composite material2O4@LiNiaCobMn(1‑a‑b)O2@MdOe(ii) a The double-coated lithium manganate composite material has the advantages of good cycling stability and manganese dissolution prevention.
Description
Technical Field
The application relates to the field of lithium manganate electrode materials, in particular to a double-coated lithium manganate composite material and a preparation method thereof.
Background
The lithium manganate with a spinel structure has the advantages of high voltage, low price, environmental friendliness, high safety performance and the like, but the high-temperature cycle performance of the lithium manganate is unstable, so that the application of the lithium manganate material in the fields of power batteries and energy storage is limited. In addition, lithium manganate is used as a power lithium ion battery anode material, and because the diffusion rate of lithium ions is low, serious polarization phenomenon exists during heavy current charging and discharging, so that the battery capacity is rapidly attenuated.
At present, the main reason why the lithium manganate material has poor high-temperature cycle performance is that the reaction of manganese element in the lithium manganate material with electrolyte is intensified under high-temperature environment, so that the manganese element is dissolved in a large amount. In order to solve the problem of manganese dissolution, patent CN 1282113A uses a liquid phase coating technology to coat LiMn2O4The surface of the particles is coated with a layer of LiCoO2Particles for preventing dissolution of manganese during charge and discharge cycles. First LiCoO2Expensive, secondly LiCoO2The electrolyte is more active and has insufficient stability, and the contact side reaction with the electrolyte in the circulation process is increased, so that the coating layer is damaged, and the circulation is influenced.
Disclosure of Invention
In order to solve the problems of easy dissolution of a manganese element and capacity attenuation of the existing lithium manganate material in the charge-discharge cycle process, the invention provides a double-coated lithium manganate composite material and a preparation method thereof.
The invention provides a double-coated lithium manganate composite material, which adopts the following technical scheme:
a double-coated lithium manganate composite material with the expression general formula of LiMn2O4@LiNiaCobMn(1-a-b)O2@MdOe；
A is the content of Ni, b is the content of Co, and 1-a-b is LiNiaCobMn(1-a-b)O2In the content of Mn, and 0<a<1，0<b<1，0<a+b<1; d is the content of a metal element M, and e is MdOeThe content of O in the solution;
the M isdOeIs Al2O3、ZrO2、SnO2、Nb2O5、V2O5One or a combination of two or more of (a) and MdOeThe content of (B) is 0.01-3 wt%.
The invention also provides a preparation method of the double-coated lithium manganate composite material, which comprises the following steps:
s1, adding MnxOyDispersing in pure water, adding ternary precursor metal salt solution, complexing agent and precipitant, heating in protective atmosphere to obtain precipitate, washing, drying, pulverizing, and sieving to obtain MnxOy@NiaCobMn(1-a-b)(OH)2Denoted as Q1; the ternary precursor metal salt solution is a mixed solution of cobalt salt, nickel salt and manganese salt;
s2, mixing and grinding Q1 and lithium salt, roasting in an oxygen or air atmosphere, crushing and sieving after roasting is finished, and obtaining LiMn2O4@LiNiaCobMn(1-a-b)O2Denoted as Q2;
s3, mixing Q2 with MdOeCarrying out mechanical fusion to obtain the LiMn of the double-coated lithium manganate composite material2O4@LiNiaCobMn(1-a-b)O2@MdOe；
The NiaCobMn(1-a-b)(OH)2Is ternaryAnd (3) precursor.
Further, the MnxOyIs MnO or MnO2、Mn3O4One or a combination of two or more of them; the Mn isxOyThe dispersion time in pure water is 30-60 min.
In S2, the lithium salt is one or a combination of two or more of lithium carbonate, lithium hydroxide, and lithium oxalate.
Further, in the S2, the lithium salt is added in an excess of 0-10% in terms of the molar ratio of the lithium salt to the Q1.
Further, in S1, the cobalt salt is one or a combination of two or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt oxalate; the nickel salt is one or the combination of more than two of nickel sulfate, nickel chloride, nickel nitrate and nickel oxalate; the manganese salt is one or the combination of more than two of manganese sulfate, manganese chloride, manganese nitrate and manganese oxalate.
Further, in the S1, MnxOyThe pH value of the mixture of the ternary precursor metal salt solution, the complexing agent and the precipitating agent is 8-12, and the heating temperature is 40-70 ℃; the protective atmosphere is one or the combination of two of nitrogen and argon.
Further, in the step S2, the grinding time is 30-240 min; during roasting, the temperature is controlled to be 400-550 ℃, the temperature is kept constant for 1-2 hours, then the temperature is controlled to be 700-1000 ℃, the temperature is kept constant for 6-18 hours, and the temperature rise rate during roasting is 1-10 ℃/min.
Further, the ternary precursor composition is one of types 111, 523, 622, 811 of NCM; the total concentration of metal ions in the solution of the ternary precursor metal salt is 1-4 mol/L.
Further, the complexing agent is ammonia water; the precipitant is NaOH or Na2CO3And KOH, or a combination of two or more thereof.
In summary, the present application has the following beneficial effects:
1. the composite material is based on lithium manganate as a core, and a coating layer is a ternary precursor and a metal oxide MdOe(ii) a The ternary precursor can improve the integral specific capacity of the lithium manganate composite material on one hand, and can prevent the lithium manganate core from being corroded by the electrolyte on the other hand; metal oxide MdOeThe coating layer can prevent the active material from directly contacting with the electrolyte, so that the electrolyte is prevented from being decomposed on the surface of the high-oxidation-state active material, and can react with a small amount of HF in the electrolyte, so that the corrosion of the HF on the lithium manganate active material is reduced, and the double coating layers have synergistic effect, so that the manganese dissolution and the decomposition of the electrolyte in the high-temperature circulation process are better prevented;
2. the ternary precursors are selected from different types, such as 111, 523, 622 and 811 in NCM, and the lithium manganate composite material coated by different ternary precursors is obtained through the ternary precursors of different types, so that the lithium manganate composite material can meet various application requirements;
3. the reversible capacity of the double-coated lithium manganate composite material can reach 135mAh/g, and the capacity retention rate can reach 98.07 percent after the double-coated lithium manganate composite material is cycled at 45 ℃ for 300 weeks.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of a lithium manganate composite material of the present invention.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples.
Examples
Example 1
S1, adding Mn3O4Dispersing in pure water for 30min, and adding 2mol/L ternary precursor metal salt solution, ammonia water and 4mol/L Na2CO3Adjusting pH of the solution to 10.85, heating at 55 deg.C in argon atmosphere to obtain precipitate, washing, drying, pulverizing, and sieving to obtain Q1; the molar ratio of the lithium manganate to the ternary shell layer is 6: 4; the ternary precursor metal salt solution is a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, and the molar ratio of nickel ions to cobalt ions to manganese ions is 1: 1: 1;
s2, mixing and ball-milling the Q1 and lithium carbonate for 60min, adding 5% of lithium carbonate in an excessive molar ratio of the lithium carbonate to the Q1, and roasting in an oxygen atmosphere during roastingFirstly controlling the temperature to be 550 ℃ and keeping the temperature for 2h, then controlling the temperature to be 980 ℃ and keeping the temperature for 10h, wherein the heating rate in roasting is 10 ℃/min, and after finishing roasting, crushing and sieving to obtain 0.6LiMn2O4@0.4LiNi1/3Co1/ 3Mn1/3O2Denoted as Q2;
s3, mixing Q2 and nano Al2O3Performing mechanical fusion for 1h, Al2O3The adding amount of the lithium manganate is 1 percent by mass, and the double-coated lithium manganate composite material 0.6LiMn is obtained2O4@0.4LiNi1/3Co1/3Mn1/3O2@Al2O3。
Example 2
S1, dispersing MnO in pure water for 40min, then adding 2mol/L ternary precursor metal salt solution, ammonia water and 4mol/L NaOH solution, adjusting the pH value to 10.35, heating at 50 ℃ in a nitrogen atmosphere to obtain a precipitate, washing, drying, crushing and sieving the precipitate to obtain Q1; the molar ratio of the lithium manganate to the ternary shell layer is 4: 6; the ternary precursor metal salt solution is a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, and the molar ratio of nickel ions to cobalt ions to manganese ions is 5: 2: 3;
s2, mixing Q1 and lithium hydroxide, ball-milling for 90min, adding 10% of lithium hydroxide according to the molar ratio of lithium to Q1, roasting in air, controlling the temperature to be 500 ℃ and keeping the temperature for 1.5h during roasting, controlling the temperature to be 920 ℃ and keeping the temperature for 10h during roasting, wherein the heating rate is 1 ℃/min during roasting, crushing and sieving after roasting is finished to obtain 0.4LiMn2O4@0.6LiNi0.5Co0.2Mn0.3O2Denoted as Q2;
s3, mixing Q2 and nano-grade ZrO2Performing mechanical fusion for 1h, ZrO2The adding amount of the lithium manganate is 3 percent by mass, and the double-coated lithium manganate composite material 0.4LiMn is obtained2O4@0.6LiNi0.5Co0.2Mn0.3O2@ZrO2。
Example 3
S1, MnO is added2Dispersing in pure water for 50min, and adding 2mol/L ternary precursorAdjusting the pH value of a bulk metal salt solution, ammonia water and a 4mol/L NaOH solution to 10.85, heating at 45 ℃ in a nitrogen atmosphere to obtain a precipitate, washing, drying, crushing and sieving the precipitate to obtain Q1; the molar ratio of the lithium manganate to the ternary shell layer is 5: 5; the ternary precursor metal salt solution is a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, and the molar ratio of nickel ions to cobalt ions to manganese ions is 6: 2: 2;
s2, mixing Q1 and lithium oxalate, ball-milling for 30min, adding 5% of lithium oxalate according to the molar ratio of lithium to Q1, roasting in air, controlling the temperature to be 480 ℃ for 2h, controlling the temperature to be 890 ℃ for 11h, controlling the heating rate to be 3 ℃/min, crushing and sieving after roasting is finished, and obtaining 0.5LiMn2O4@0.5LiNi0.6Co0.2Mn0.2O2Denoted as Q2;
s3, mixing Q2 and nano SnO2Mechanical fusion for 1h, SnO2The adding amount of the lithium manganate is 1.5 percent by mass, and the double-coated lithium manganate composite material 0.5LiMn is obtained2O4@0.5LiNi0.6Co0.2Mn0.2O2@SnO2。
Example 4
S1, adding Mn3O4Dispersing in pure water for 60min, then adding 2mol/L ternary precursor metal salt solution, ammonia water and 4mol/L NaOH solution, adjusting the pH value to 10.55, heating at 60 ℃ in a nitrogen atmosphere to obtain a precipitate, washing, drying, crushing and sieving the precipitate to obtain Q1; the molar ratio of the lithium manganate to the ternary shell layer is 6.5: 3.5; the ternary precursor metal salt solution is a mixed solution of cobalt chloride, nickel chloride and manganese chloride, and the molar ratio of nickel ions to cobalt ions to manganese ions is 8: 1: 1;
s2, mixing Q1 and lithium hydroxide, ball-milling for 120min, adding lithium hydroxide according to the molar ratio of lithium to Q1 and the molar ratio of 2.5% excess, roasting in oxygen, controlling the temperature to be 530 ℃ for 1h, controlling the temperature to be 750 ℃ for 12h, controlling the heating rate to be 4 ℃/min, crushing and sieving after roasting is completed to obtain 0.65LiMn2O4@0.35LiNi0.8Co0.1Mn0.1O2Denoted as Q2;
s3, mixing Q2 and nano Nb2O5Performing mechanical fusion for 1h, Nb2O5The adding amount of the lithium manganate is 0.5 percent by mass ratio, and the double-coated lithium manganate composite material 0.65LiMn is obtained2O4@0.35LiNi0.8Co0.1Mn0.1O2@Nb2O5。
Example 5
S1, adding Mn3O4Dispersing in pure water for 55min, then adding 2mol/L ternary precursor metal salt solution, ammonia water and 4mol/L Na2CO3Adjusting pH of the solution to 10.9, heating at 70 deg.C in argon atmosphere to obtain precipitate, washing, drying, pulverizing, and sieving to obtain Q1; the molar ratio of the lithium manganate to the ternary shell layer is 5.5: 4.5; the ternary precursor metal salt solution is a mixed solution of cobalt nitrate, nickel nitrate and manganese nitrate, and the molar ratio of nickel ions to cobalt ions to manganese ions is 6: 2: 2;
s2, mixing Q1 and lithium carbonate, ball-milling for 120min, adding 7.5% of lithium carbonate according to the molar ratio of lithium to Q1, roasting in air, controlling the temperature to be 540 ℃ and keeping the temperature for 1.5h, controlling the temperature to be 910 ℃ and keeping the temperature for 9.5h, controlling the heating rate to be 5 ℃/min, crushing and sieving after roasting is finished, and obtaining 0.55LiMn2O4@0.45LiNi0.6Co0.2Mn0.2O2Denoted as Q2;
s3, mixing Q2 with nano-scale V2O5Performing mechanical fusion for 1h, V2O5The adding amount of the lithium manganate is 0.75 percent by mass ratio, and the double-coated lithium manganate composite material 0.55LiMn is obtained2O4@0.45LiNi0.6Co0.2Mn0.2O2@V2O5。
Example 6
S1, MnO is added2Dispersing in pure water for 45min, adding 2mol/L ternary precursor metal salt solution, ammonia water and 4mol/L NaOH solution, adjusting pH to 8, and heating at 70 deg.C in nitrogen atmosphere to obtain precipitatePrecipitating, washing, drying, pulverizing, and sieving to obtain Q1; the molar ratio of the lithium manganate to the ternary shell layer is 7: 3; the ternary precursor metal salt solution is a mixed solution of nickel oxalate, cobalt oxalate and manganese oxalate, and the molar ratio of nickel ions to cobalt ions to manganese ions is 6: 2: 2;
s2, mixing Q1 and lithium oxalate, ball-milling for 30min, adding lithium oxalate according to the molar ratio of lithium to Q1 and the excessive 4.5 percent of lithium, roasting in air, controlling the temperature to be 400 ℃ for 2h, controlling the temperature to be 930 ℃ for 9h, controlling the heating rate to be 5 ℃/min, crushing and sieving after roasting is finished, and obtaining 0.7LiMn2O4@0.3LiNi0.6Co0.2Mn0.2O2Denoted as Q2;
s3, mixing Q2 and nano SnO2Mechanical fusion for 1h, SnO2The adding amount of the lithium manganate is 1.25 percent by mass ratio, and the double-coated lithium manganate composite material 0.7LiMn is obtained2O4@0.3LiNi0.6Co0.2Mn0.2O2@SnO2。
Example 7
S1, adding Mn3O4Dispersing in pure water for 35min, then adding 1mol/L ternary precursor metal salt solution, ammonia water and 4mol/L KOH solution, adjusting the pH value to 12, heating at 65 ℃ in an argon atmosphere to obtain a precipitate, washing, drying, crushing and sieving the precipitate to obtain Q1; the molar ratio of the lithium manganate to the ternary shell layer is 6.5: 3.5; the ternary precursor metal salt solution is a mixed solution of cobalt chloride, nickel chloride and manganese chloride, and the molar ratio of nickel ions to cobalt ions to manganese ions is 6: 2: 2;
s2, mixing Q1 and lithium carbonate, ball-milling for 120min, adding 5% of lithium carbonate according to the molar ratio of lithium to Q1, roasting in air, controlling the temperature to be 500 ℃ for 2h, controlling the temperature to be 1000 ℃ for 6h, controlling the heating rate to be 5 ℃/min, crushing and sieving after roasting is finished, and obtaining 0.65LiMn2O4@0.35LiNi0.6Co0.2Mn0.2O2Denoted as Q2;
s3, mixing Q2 and nano Nb2O5Performing mechanical fusion for 1h, Nb2O5The adding amount of the lithium manganate is 1.45 percent by mass ratio, and the double-coated lithium manganate composite material 0.65LiMn is obtained2O4@0.35LiNi0.6Co0.2Mn0.2O2@Nb2O5。
Example 8
S1, adding Mn3O4Dispersing in pure water for 55min, then adding 4mol/L ternary precursor metal salt solution, ammonia water and 4mol/L NaOH solution, adjusting the pH value to 10.95, heating at 50 ℃ in an argon atmosphere to obtain a precipitate, washing, drying, crushing and sieving the precipitate to obtain Q1; the molar ratio of the lithium manganate to the ternary shell layer is 6: 4; the ternary precursor metal salt solution is a mixed solution of nickel sulfate, cobalt sulfate and manganese sulfate, and the molar ratio of nickel ions to cobalt ions to manganese ions is 6: 2: 2;
s2, mixing Q1 and lithium carbonate, ball-milling for 240min, adding 6% of lithium carbonate in an excessive manner according to the molar ratio of the lithium carbonate to Q1, roasting in an oxygen atmosphere, controlling the temperature to be 520 ℃ and keeping the temperature for 1.5h during roasting, controlling the temperature to be 700 ℃ and keeping the temperature for 18h, controlling the heating rate to be 5 ℃/min during roasting, crushing and sieving after roasting is completed, and obtaining 0.6LiMn2O4@0.4LiNi0.6Co0.2Mn0.2O2Denoted as Q2;
s3, mixing Q2 and nano Al2O3Performing mechanical fusion for 1h, Al2O3The adding amount of the lithium manganate is 2 percent by mass, and the double-coated lithium manganate composite material 0.6LiMn is obtained2O4@0.4LiNi0.6Co0.2Mn0.2O2@Al2O3。
Example 9
S1, adding Mn3O4Dispersing in pure water for 35min, then adding 2mol/L ternary precursor metal salt solution, ammonia water and 4mol/L NaOH solution, adjusting the pH value to 10.65, heating at 65 ℃ in a nitrogen atmosphere to obtain a precipitate, washing, drying, crushing and sieving the precipitate to obtain Q1; the molar ratio of the lithium manganate to the ternary shell layer is 4.5: 5.5; the ternary precursor metal salt solution is nickel sulfate,The mixed solution of cobalt sulfate and manganese sulfate, wherein the molar ratio of nickel ions to cobalt ions to manganese ions is 6: 2: 2;
s2, mixing Q1 and lithium hydroxide, ball-milling for 120min, adding lithium hydroxide according to the molar ratio of lithium to Q1 of 8.5% excess, roasting in air, controlling the temperature to be 550 ℃ for 2h, controlling the temperature to be 910 ℃ for 13h, controlling the heating rate to be 5 ℃/min, crushing and sieving after roasting is finished, and obtaining 0.45LiMn2O4@0.55LiNi0.6Co0.2Mn0.2O2Denoted as Q2;
s3, mixing Q2 and nano-grade ZrO2Performing mechanical fusion for 1h, ZrO2The adding amount of the lithium manganate is 2.6 percent by mass, and the double-coated lithium manganate composite material 0.45LiMn is obtained2O4@0.55LiNi0.6Co0.2Mn0.2O2@ZrO2。
Comparative example
Comparative example 1
Weighing Mn3O4130.94g and Li2CO3And (3) directly performing ball milling and mixing on 63.43g of the lithium manganate anode material for 1h, then controlling the temperature to be 500 ℃ and keeping the temperature for 2h, then controlling the temperature to be 800 ℃ and keeping the temperature for 12h, and heating the mixture at a rate of 5 ℃/min during roasting to obtain the lithium manganate anode material.
Comparative example 2
Weighing 60g of lithium manganate and 40g of 622 type ternary precursor, and mixing in a VC mixer for 1h to obtain the composite cathode material
Performance test
The double-coated lithium manganate composite materials prepared in examples 1-9 and the lithium manganate composite materials prepared in comparative examples 1-2 are subjected to 300 charge-discharge cycle experiments at 45 ℃, and the capacity retention rate of a sample after the experiment is calculated, wherein the capacity retention rate is the ratio of the capacity before the experiment to the capacity after the experiment. The results of the experiment are shown in table 1.
TABLE 1
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The double-coated lithium manganate composite material is characterized in that the general expression formula of the double-coated lithium manganate composite material is LiMn2O4@LiNiaCobMn(1-a-b)O2@MdOe；
A is the content of Ni, b is the content of Co, and 1-a-b is LiNiaCobMn(1-a-b)O2In the content of Mn, and 0<a<1，0<b<1，0<a+b<1; d is the content of a metal element M, and e is MdOeThe content of O in the solution;
the M isdOeIs Al2O3、ZrO2、SnO2、Nb2O5、V2O5One or a combination of two or more of (a) and MdOeThe content of (B) is 0.01-3 wt%.
2. A method for preparing the double-coated lithium manganate composite material as described in claim 1, comprising the steps of:
s1, adding MnxOyDispersing in pure water, adding ternary precursor metal salt solution, complexing agent and precipitant, heating in protective atmosphere to obtain precipitate, washing, drying, pulverizing, and sieving to obtain MnxOy@NiaCobMn(1-a-b)(OH)2Denoted as Q1; the ternary precursor metal salt solution is a mixed solution of cobalt salt, nickel salt and manganese salt;
s2, mixing and grinding Q1 and lithium salt, roasting in an oxygen or air atmosphere, crushing and sieving after roasting is finished, and obtaining LiMn2O4@LiNiaCobMn(1-a-b)O2Denoted as Q2;
s3, mixing Q2 with MdOeCarrying out mechanical fusion to obtain the LiMn of the double-coated lithium manganate composite material2O4@LiNiaCobMn(1-a-b)O2@MdOe；
The NiaCobMn(1-a-b)(OH)2Is a ternary precursor.
3. The method of claim 2, wherein the Mn is present in an amount sufficient to form a double-coated lithium manganate composite materialxOyIs MnO or MnO2、Mn3O4One or a combination of two or more of them; the Mn isxOyThe dispersion time in pure water is 30-60 min.
4. The method according to claim 2, wherein in the step S2, the lithium salt is one or a combination of two or more of lithium carbonate, lithium hydroxide and lithium oxalate.
5. The method for preparing the double-coated lithium manganate composite material as claimed in claim 2, wherein in said S2, the lithium salt is added in an excess of 0-10% in terms of the molar ratio of lithium salt to Q1.
6. The method for preparing a double-coated lithium manganate composite material as claimed in claim 2, wherein in said S1, said cobalt salt is one or a combination of two or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt oxalate; the nickel salt is one or the combination of more than two of nickel sulfate, nickel chloride, nickel nitrate and nickel oxalate; the manganese salt is one or the combination of more than two of manganese sulfate, manganese chloride, manganese nitrate and manganese oxalate.
7. The method for preparing the double-coated lithium manganate composite material as claimed in claim 2, wherein in S1, Mn is addedxOyThe pH value of the mixture of the ternary precursor metal salt solution, the complexing agent and the precipitating agent is 8-12, and the heating temperature is 40-70 ℃; the protective atmosphere is one or the combination of two of nitrogen and argon.
8. The method for preparing the double-coated lithium manganate composite material as claimed in claim 2, wherein in S2, the grinding time is 30-240 min; during roasting, the temperature is controlled to be 400-550 ℃, the temperature is kept constant for 1-2 hours, then the temperature is controlled to be 700-1000 ℃, the temperature is kept constant for 6-18 hours, and the temperature rise rate during roasting is 1-10 ℃/min.
9. The method for preparing the double-coated lithium manganate composite material as described in claim 2, wherein said ternary precursor composition is one of NCM types 111, 523, 622, 811; the total concentration of metal ions in the solution of the ternary precursor metal salt is 1-4 mol/L.
10. The method for preparing a double-coated lithium manganate composite material according to any of claims 1 to 8, wherein said complexing agent is ammonia; the precipitant is NaOH or Na2CO3And KOH, or a combination of two or more thereof.
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| CN109830651A (en) * | 2017-11-23 | 2019-05-31 | 天津国安盟固利新材料科技股份有限公司 | A kind of tertiary cathode high-nickel material and preparation method thereof that double-coating is modified |
| CN111342024A (en) * | 2020-03-16 | 2020-06-26 | 陕西海恩新材料有限责任公司 | Long-cycle lithium manganate positive electrode material and preparation method thereof |
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| CN104953109A (en) * | 2015-05-11 | 2015-09-30 | 中信国安盟固利电源技术有限公司 | Core-shell-structure lithium manganate capable of improving high temperature resistance performance, and synthesis method of core-shell-structure lithium manganate |
| CN109830651A (en) * | 2017-11-23 | 2019-05-31 | 天津国安盟固利新材料科技股份有限公司 | A kind of tertiary cathode high-nickel material and preparation method thereof that double-coating is modified |
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