CN112242510A - Preparation method and application of epitaxial growth layer and sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material - Google Patents
Preparation method and application of epitaxial growth layer and sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 89
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 84
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 150000002641 lithium Chemical class 0.000 title claims abstract description 49
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 title claims description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 38
- 239000010406 cathode material Substances 0.000 claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract 5
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract 5
- 229910052751 metal Inorganic materials 0.000 claims description 49
- 239000002184 metal Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 29
- 239000012266 salt solution Substances 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 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 6
- 238000003756 stirring Methods 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 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 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 239000012300 argon atmosphere Substances 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 238000001238 wet grinding Methods 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 46
- 239000010405 anode material Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 22
- 239000000463 material Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 229910052979 sodium sulfide Inorganic materials 0.000 description 10
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- -1 have been developed2 Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 1
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 1
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- 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
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- 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
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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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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
本发明公开了一种外延生长层和硫钠晶格改性富锂锰基正极材料的制备方法及应用。本发明提供的外延生长层和硫钠晶格改性富锂锰基正极材料的制备方法简单，后处理容易，成本低，制备得到的正极材料的颗粒尺寸分布均匀，其0.1C首圈放电比容量为304.69mAh g‑1，5C的放电比容量为129.43mAh g‑1，1C循环200圈的容量保持率为93.31％，不仅首圈放电比容量、倍率性能和循环性能均有显著的提升，而且有效的缓解了电压的衰减；因此，本发明制备得到的外延生长层和硫钠晶格改性富锂锰基正极材料在制备锂离子电池中的应用前景广泛。
The invention discloses a preparation method and application of an epitaxial growth layer and a lithium-rich manganese-based positive electrode material modified by a sodium sulfate lattice. The preparation method of the epitaxial growth layer and the sodium sulfate lattice modified lithium-rich manganese-based positive electrode material provided by the invention is simple, the post-processing is easy, the cost is low, the particle size distribution of the prepared positive electrode material is uniform, and the 0.1C first cycle discharge ratio is The capacity is 304.69mAh g -1 , the discharge specific capacity at 5C is 129.43mAh g -1 , and the capacity retention rate of 200 cycles at 1C is 93.31%. Not only the specific capacity, rate performance and cycle performance of the first cycle are significantly improved, Moreover, the attenuation of the voltage is effectively alleviated; therefore, the epitaxial growth layer and the sodium sulfate lattice modified lithium-rich manganese-based cathode material prepared by the present invention have wide application prospects in the preparation of lithium ion batteries.
Description
Technical Field
The invention belongs to the technical field of battery anode materials. More particularly, relates to a preparation method and application of an epitaxial growth layer and a sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material.
Background
With the accelerated consumption of fossil energy, problems of global warming and environmental pollution have created serious challenges for the development of modern society. The development of sustainable clean energy is a necessary way for the development of the future society. Thus, new clean renewable energy sources are being sought to reduce the dependence on fossil energy. Solar energy, water energy, wind energy, geothermal energy and other clean energy resources are widely concerned by people. The development of new energy sources continuously drives the progress of the energy storage field. Lithium ion batteries stand out due to the advantages of high energy density, excellent energy conversion efficiency, long cycle life, and the like. However, a critical component that determines the performance of lithium ion batteries is the positive electrode material.
Currently, a series of lithium ion positive electrode materials, such as LiCoO, have been developed2、LiNi0.8Co0.15Al0.05O2(NCA)、LiNixCoy MnzO2(NCM; x + y + z ═ 1), spinel LiMn2O4And olivine LiFePO4And has been widely used commercially. However, these materials still do not meet the increasing demand for energy density of lithium ion batteries. Lithium-rich manganese-based layered oxide positive electrode material, xLi2MnO3·(1-x)LiMO2(0<x<1, M ═ Mn, Co, Ni), due to its high specific capacity (>250mAh g-1) High voltage and low price, and the like, has attracted great research interest, and is considered as the most potential lithium ion battery anode material of the next generationOne (Zhang Yidi, preparation of layered lithium-rich manganese-based lithium ion battery anode material and electrochemical performance thereof, Zhejiang university, 2016). However, such materials have low first-turn coulombic efficiency, sharply attenuated capacity and average voltage, and poor rate performance, which hinder industrialization and application of such materials, and a solution is needed. Therefore, the development of the modified lithium-rich manganese-based positive electrode material with excellent specific discharge capacity, smaller voltage attenuation, outstanding stability and rate capability has extremely important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of poor cycle performance, rapid voltage attenuation and low rate performance of the conventional modified lithium-rich manganese-based anode material, and provides a preparation method and application of an epitaxial growth layer and a sulfur-sodium lattice modified lithium-rich manganese-based anode material.
The invention aims to provide a preparation method of an epitaxial growth layer and a sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material.
The invention also aims to provide application of the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material prepared by the method in preparation of a lithium ion battery.
The above purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of an epitaxial growth layer and a sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material, which comprises the following steps:
s1, fully dissolving a manganese source, a nickel source and a cobalt source in deionized water to obtain a mixed metal salt solution;
s2, adding an ammonia water solution into the mixed metal salt solution obtained in the step S1, adjusting the pH to 7-9 by using an inorganic base, stirring for coprecipitation reaction, filtering, washing and drying to obtain a lithium-rich manganese-based layered oxide precursor;
s3, mixing the precursor obtained in the step S2 with a lithium source, calcining at 480-520 ℃ for 5.5-6.5 h, calcining at 840-920 ℃ for 11.5-12.5 h, and grinding to obtain a lithium-rich manganese-based layered oxide cathode material;
s4, mixing the positive electrode material obtained in the step S3 with Na2S is put into ethanol solution, ground by a wet method and evaporated to dryness to obtain Na2S-coated lithium-rich manganese-based layered oxide cathode material;
and S5, calcining the anode material obtained in the step S4 at 300-700 ℃ for 5.5-6.5 h in an argon environment, and washing with water for 3-5 times to obtain an epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based anode material.
In the invention, the lithium-rich manganese-based layered oxide cathode material and Na are mixed2S is ground by a wet method, evaporated to dryness and then calcined in an inert atmosphere, and Na is arranged on the surface layer of the secondary particles2Mn(SO4)2The (C2/C) phase, C2/C and R-3m/C2/m have similar oxygen frameworks, can achieve atomic level combination, improve the stability of the (C2/C) phase, simultaneously can avoid direct contact of secondary particles and electrolyte, reduce the occurrence of side reactions and further improve the cycle life of the material; at the same time, a strong Mn-O-Na bond is formed, and the diffusion and dissolution loss of Mn ions are suppressed, thereby preventing the structural transformation (the transformation of the layered structure into the spinel or rock salt structure). On the other hand, during calcination, part of Na+Doping into the lithium layer due to Na+Radius ratio of (Li)+The radius of the lithium layer is large, which is beneficial to enlarging the crystal face spacing of the lithium layer and improving the rate capability; at the same time, S is on the surface of the material2-By substitution of part O2-The oxygen partial pressure on the surface is reduced, and the precipitation of oxygen is inhibited under the high-voltage charge and discharge; in addition, S2-Has strong reducibility, partial reduction of transition metal elements, Mn4+Reduction of (2) is advantageous for activating Li2MnO3And the discharge capacity is improved. At the same time, sulfate (surface inert Na) is formed on the surface of the material2SO4Water washing is carried out to remove), oxygen atoms competing for a bulk phase are captured, oxygen vacancies are formed on the surface of the material, and the oxygen release is inhibited, so that the structure of the material is stabilized.
Preferably, the calcination conditions in step S3 are: calcining at 450 ℃ for 6h and then calcining at 850 ℃ for 12 h.
Preferably, the calcination conditions in step S5 are: calcining at 400 ℃ for 6 h.
Preferably, the molar ratio of the manganese source, the nickel source and the cobalt source in the lithium-rich manganese-based layered oxide precursor in the step S2 is 50-60: 10-15.
More preferably, the molar ratio of the manganese source, the nickel source and the cobalt source in the lithium-rich manganese-based layered oxide precursor in the step S2 is 54:13: 13.
Preferably, the molar ratio of the metal and the ammonia water in the mixed metal salt solution in the step S2 is 10: 1-3.
More preferably, the molar ratio of the metal and the ammonia water in the mixed metal salt solution in the step S2 is 5: 1.
Preferably, the concentration of the ammonia water solution in the step S2 is 1-2 mol/L.
More preferably, the concentration of the aqueous ammonia solution in the step S2 is 1.2 mol/L.
Preferably, the molar ratio of the metal in the precursor in the step S3 to the lithium source is 1: 1.41-1.5.
More preferably, the molar ratio of the metal in the precursor of step S3 to the lithium source is 1: 1.41.
Preferably, the cathode material and Na in step S42The mass ratio of S is 0.01-0.06: 1.
More preferably, the cathode material and Na in step S42The mass ratio of S is 0.03: 1.
Conventional sources of manganese, nickel and cobalt may be used in the present invention. Preferably, the manganese source in step S1 is any one or more of manganese acetate, manganese nitrate or manganese sulfate; the nickel source is any one or more of nickel acetate, nickel nitrate or nickel sulfate; the cobalt source is any one or more of cobalt acetate, cobalt nitrate or cobalt sulfate.
More preferably, the manganese source of step S1 is manganese acetate; the nickel source is nickel acetate; the cobalt source is cobalt acetate.
Preferably, in step S3, the lithium source is any one or more of lithium nitrate, lithium carbonate, lithium hydroxide, and lithium bicarbonate.
More preferably, the lithium source in step S3 is lithium nitrate.
Preferably, the concentration of the metal in the mixed metal salt solution in the step S1 is 1.8-2.2 mol/L.
More preferably, the concentration of the metal in the mixed metal salt solution of step S1 is 2 mol/L.
Preferably, the pH of the mixed metal salt solution of step S2 is 8.
Preferably, the concentration of the inorganic base in the step S2 is 1.8-2.2 mol/L.
More preferably, the concentration of the inorganic base in the step S2 is 2 mol/L.
Preferably, the inorganic base in step S2 is Na2CO3。
The epitaxial growth layer and the sulfur-sodium crystal lattice modified lithium-rich manganese-based positive electrode material prepared by the method are uniform in particle size distribution, and a battery assembled by the positive electrode material is subjected to electrical performance test at the test temperature of 25 ℃ and the test voltage range of 2.0-4.8V, and the first-loop discharge specific capacity of 0.1C is 304.69mAh g-1And the specific discharge capacity of 5C is 129.43mAh g-1The capacity retention rate of 200 cycles of 1C cycle is 93.31%, and the voltage retention rate is 88.20%, which shows that the cathode material has excellent electrochemical performance; therefore, the application of the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material prepared by the method in the preparation of the lithium ion battery also falls within the protection scope of the invention.
The invention has the following beneficial effects:
the invention provides a preparation method and application of an epitaxial growth layer and a sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material. The epitaxial growth layer and the sulfur-sodium crystal lattice modified lithium-rich manganese-based positive electrode material prepared by the method have uniform particle size distribution, and the specific discharge capacity of the first circle of 0.1C is 304.69mAh g-1And the specific discharge capacity of 5C is 129.43mAh g-1The capacity retention rate of 200 cycles of 1C cycle is 93.31%, the discharge specific capacity, the rate capability and the cycle performance of the first cycle are obviously improved, and the voltage attenuation is effectively relieved; the preparation method is simple, the post-treatment is easy, and the cost is low; therefore, the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material prepared by the method have application prospects in preparation of lithium ion batteriesIs wide in application.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of an epitaxial growth layer and a sulfur-sodium lattice modified lithium-rich manganese-based cathode material prepared by the method.
FIG. 2 is an SEM image of an epitaxial growth layer and a sulfur-sodium lattice modified lithium-rich manganese-based cathode material prepared by the method.
FIG. 3 is a TEM image of the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based cathode material prepared by the invention.
FIG. 4 is a 0.1C charge-discharge curve diagram of the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material prepared by the method at the test temperature of 25 ℃ and the test voltage of 2.0-4.8V.
FIG. 5 is a 1C cycle performance diagram of the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material prepared by the method at a test temperature of 25 ℃ and a test voltage of 2.0-4.8V.
FIG. 6 is a rate performance graph of 0.1C, 0.5C, 1C, 3C and 5C of the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based anode material prepared by the method at a test temperature of 25 ℃ and a test voltage of 2.0-4.8V.
FIG. 7 is a graph of the average discharge voltage performance of the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material prepared by the method at the test temperature of 25 ℃ and the test voltage of 2.0-4.8V.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1 preparation of epitaxially grown layer and sulfur-sodium lattice-modified lithium-rich manganese-based cathode material
A preparation method of an epitaxial growth layer and a sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material comprises the following steps:
s1, fully dissolving manganese acetate, nickel acetate and cobalt acetate in deionized water to obtain a mixed metal salt solution (the concentration of metal in the mixed metal salt solution is 2 mol/L);
s2, adding an ammonia water solution (the molar ratio of the metal in the mixed metal salt solution to the ammonia water is 5:1, and the concentration of the ammonia water solution is 1.2mol/L) into the mixed metal salt solution obtained in the step S1, and then adding Na2CO3(the concentration is 2mol/L) adjusting the pH value to 8, stirring for coprecipitation reaction, filtering, washing and drying to obtain a lithium-rich manganese-based layered oxide precursor (the molar ratio of manganese acetate, nickel acetate and cobalt acetate in the precursor is 54:13: 13);
s3, mixing the precursor obtained in the step S2 with lithium nitrate (the molar ratio of metal in the precursor to the lithium nitrate is 1:1.41), calcining at 450 ℃ for 6 hours, calcining at 850 ℃ for 12 hours, and grinding to obtain a lithium-rich manganese-based layered oxide cathode material;
s4, mixing the positive electrode material obtained in the step S3 with Na2S (cathode material and Na)2The mass ratio of S is 0.03:1) is put into an ethanol solution, ground by a wet method and evaporated to dryness to obtain Na2S-coated lithium-rich manganese-based layered oxide cathode material;
and S5, calcining the anode material obtained in the step S4 at 400 ℃ for 6h in an argon environment, and washing with water for 4 times to obtain the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based anode material.
Example 2 preparation of epitaxially grown layer and sulfur-sodium lattice modified lithium-rich manganese-based cathode Material
A preparation method of an epitaxial growth layer and a sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material comprises the following steps:
s1, fully dissolving manganese nitrate, nickel nitrate and cobalt nitrate in deionized water to obtain a mixed metal salt solution (the concentration of metal in the mixed metal salt solution is 1.8 mol/L);
s2, adding an ammonia water solution (the molar ratio of the metal in the mixed metal salt solution to the ammonia water is 10: 3, and the concentration of the ammonia water solution is 1mol/L) into the mixed metal salt solution obtained in the step S1, and then adding Na2CO3(concentration is 2.2mol/L) adjusting pH to 7, stirring for coprecipitation reaction, filtering, washing, drying,obtaining a lithium-rich manganese-based layered oxide precursor (the molar ratio of manganese nitrate, nickel nitrate and cobalt nitrate in the precursor is 4:1: 1);
s3, mixing the precursor obtained in the step S2 with lithium carbonate (the molar ratio of metal in the precursor to the lithium carbonate is 1:1.41), calcining at 520 ℃ for 5.5h, calcining at 920 ℃ for 11.5h, and grinding to obtain a lithium-rich manganese-based layered oxide cathode material;
s4, mixing the positive electrode material obtained in the step S3 with Na2S (cathode material and Na)2The mass ratio of S is 0.01:1) is put into an ethanol solution, ground by a wet method and evaporated to dryness to obtain Na2S-coated lithium-rich manganese-based layered oxide cathode material;
and S5, calcining the anode material obtained in the step S4 at 700 ℃ for 5.5h in an argon environment, and washing with water for 5 times to obtain an epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based anode material.
Example 3 preparation of epitaxially grown layer and sulfur-sodium lattice modified lithium-rich manganese-based cathode material
A preparation method of an epitaxial growth layer and a sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material comprises the following steps:
s1, fully dissolving manganese sulfate, nickel sulfate and cobalt sulfate in deionized water to obtain a mixed metal salt solution (the concentration of metal in the mixed metal salt solution is 2.2 mol/L);
s2, adding an ammonia water solution (the molar ratio of the metal in the mixed metal salt solution to the ammonia water is 10: 1, and the concentration of the ammonia water solution is 2mol/L) into the mixed metal salt solution obtained in the step S1, and then adding Na2CO3(the concentration is 1.8mol/L) adjusting the pH value to 9, stirring for coprecipitation reaction, filtering, washing and drying to obtain a lithium-rich manganese-based layered oxide precursor (the molar ratio of manganese sulfate, nickel sulfate and cobalt sulfate in the precursor is 5:1: 1);
s3, mixing the precursor obtained in the step S2 with lithium hydroxide (the molar ratio of metal in the precursor to the lithium hydroxide is 1:1.5), calcining at 480 ℃ for 6.5h, calcining at 840 ℃ for 12.5h, and grinding to obtain a lithium-rich manganese-based layered oxide cathode material;
s4, mixing the positive electrode material obtained in the step S3 with Na2S (cathode material and Na)2S with the mass ratio of 0.06:1) is put into an ethanol solution, ground by a wet method and evaporated to dryness to obtain Na2S-coated lithium-rich manganese-based layered oxide cathode material;
and S5, calcining the anode material obtained in the step S4 at 300 ℃ for 6.5h in an argon environment, and washing with water for 3 times to obtain an epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based anode material.
Example 4 preparation of epitaxially grown layer and sulfur-sodium lattice modified lithium-rich manganese-based cathode material
A preparation method of an epitaxial growth layer and a sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material comprises the following steps:
s1, fully dissolving manganese acetate, nickel nitrate and cobalt sulfate in deionized water to obtain a mixed metal salt solution (the concentration of metal in the mixed metal salt solution is 1.8 mol/L);
s2, adding an ammonia water solution (the molar ratio of the metal in the mixed metal salt solution to the ammonia water is 10: 3, and the concentration of the ammonia water solution is 2mol/L) into the mixed metal salt solution obtained in the step S1, and then adding Na2CO3(the concentration is 2.2mol/L) adjusting the pH value to 9, stirring for coprecipitation reaction, filtering, washing and drying to obtain a lithium-rich manganese-based layered oxide precursor (the molar ratio of manganese acetate, nickel nitrate and cobalt sulfate in the precursor is 54:13: 13);
s3, mixing the precursor obtained in the step S2 with lithium bicarbonate (the molar ratio of metal in the precursor to the lithium bicarbonate is 1:1.41), calcining at 480 ℃ for 5.5h, calcining at 840 ℃ for 11.5h, and grinding to obtain a lithium-rich manganese-based layered oxide cathode material;
s4, mixing the positive electrode material obtained in the step S3 with Na2S (cathode material and Na)2S with the mass ratio of 0.06:1) is put into an ethanol solution, ground by a wet method and evaporated to dryness to obtain Na2S-coated lithium-rich manganese-based layered oxide cathode material;
and S5, calcining the anode material obtained in the step S4 at 300 ℃ for 5.5h in an argon environment, and washing with water for 3 times to obtain an epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based anode material.
Application example 1 Performance test of epitaxial growth layer and Sulfur-sodium lattice modified lithium-rich manganese-based cathode Material
1. Experimental methods
Taking example 1 as an example, the epitaxial growth layer prepared in example 1, the sulfur-sodium lattice modified lithium-rich manganese-based cathode material, acetylene black and PVDF were mixed and coated on an aluminum foil as a cathode electrode, a metal lithium sheet as an anode electrode, a microporous polypropylene film as a separator, and 1mol L of acetylene black and PVDF were mixed and coated on the aluminum foil as a cathode electrode, the microporous polypropylene film as a separator-1LiPF of6(the solvent is V)EC:VDEC1:1) as an electrolyte, assembling a lithium ion battery (CR2025 button cell) according to the sequence of a positive electrode shell, a positive electrode, a diaphragm, a negative electrode and a negative electrode shell, and testing the electrochemical performance of the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material prepared by the invention.
And (3) carrying out X-ray diffraction analysis, scanning electron microscope analysis and transmission electron microscope analysis on the epitaxial growth layer and the sodium-sulfur lattice modified lithium-rich manganese-based positive electrode material prepared in the embodiment 1, and carrying out electrical property test at the test temperature of 25 ℃ and the test voltage of 2.0-4.8V.
2. Results of the experiment
The epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based positive electrode material are prepared. The XRD, SEM and TEM images of the material are shown in figures 1-3 in sequence. FIG. 1 is a drawing in which 3% Na is introduced2The XRD pattern of the lithium-rich manganese-based anode material of S is compared with the database and is alpha-NaFeO2The structure comprises a hexagonal layered structure with a space group of R-3m, and when 2 theta is approximately equal to 20-30 degrees, the hexagonal layered structure corresponds to a monoclinic C2/m crystal phase. There is a weak abnormal peak in the XRD pattern at a position approximately 2 theta ≈ 32 DEG, compared with the standard card, Na2Mn(SO4)2A crystalline phase. The SEM image of the modified lithium-rich cathode material shows that a layer of compact coating appears on the surface of the secondary particles, and the result of XRD shows that the coating is Na2Mn(SO4)2And (4) coating. From a more microscopic HRTEM discussion, the primary particles appeared in different crystal phases from the inner R-3m crystal image, through the transition layer, to the surface C2/C phase, C2/C corresponding to Na2Mn(SO4)2A crystalline phase. The synthesis proves that the epitaxial growth layer and the sulfur-sodium crystal lattice modified lithium-rich manganese-based positive electrode prepared by the inventionA pole material.
The charge-discharge curve chart of 0.1C of the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based anode material prepared by the method is shown in figure 4 when the test temperature is 25 ℃ and the test voltage is 2.0-4.8V, and it can be seen that the specific discharge capacity of the first circle of 0.1C of the anode material is 304.69mAh g-1。
The cycle performance diagram of the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based anode material at 1C under the test temperature of 25 ℃ and the test voltage of 2.0-4.8V is shown in FIG. 5, and it can be seen that the capacity retention ratio of the anode material at 200 cycles of 1C is 93.31%.
The multiplying power performance graphs of 0.1C, 0.5C, 1C, 3C and 5C of the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based anode material prepared by the method disclosed by the invention at the test temperature of 25 ℃ and the test voltage of 2.0-4.8V are shown in figure 6, and it can be seen that the specific capacity of the anode material at 5C is 129.43mAh g-1。
The average discharge voltage performance diagram of the epitaxial growth layer and the sulfur-sodium lattice modified lithium-rich manganese-based anode material prepared by the invention at the test temperature of 25 ℃ and the test voltage of 2.0-4.8V is shown in FIG. 7, and it can be seen that the average discharge voltage retention ratio of the anode material is 88.20%.
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)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113113586A (en) * | 2021-04-07 | 2021-07-13 | 浙江大学 | Positive electrode for lithium ion battery and preparation method and application thereof |
| EP4318667A4 (en) * | 2021-08-25 | 2025-04-30 | SM Lab Co., Ltd. | Positive electrode active material, method for preparing same, and lithium secondary battery including positive electrode comprising same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2828202A1 (en) * | 2012-03-21 | 2015-01-28 | The Gillette Company | Methods of making metal-doped nickel oxide active materials |
| CN104617253A (en) * | 2015-02-02 | 2015-05-13 | 吉林大学 | Method for preparing sulfur composite electrodes |
| CN104659344A (en) * | 2015-01-30 | 2015-05-27 | 东南大学 | Lithium-site doped and metal oxide-coated lithium ion battery positive electrode material and preparation method thereof |
| CN106898775A (en) * | 2015-12-18 | 2017-06-27 | 国联汽车动力电池研究院有限责任公司 | Double cladded type richness lithium materials in a kind of surface and preparation method thereof |
| CN109256557A (en) * | 2018-10-23 | 2019-01-22 | 乳源东阳光磁性材料有限公司 | Nickelic layered oxide lithium electricity positive electrode of a kind of perofskite type oxide cladding and preparation method thereof |
| CN110783553A (en) * | 2019-11-26 | 2020-02-11 | 长虹格兰博科技股份有限公司 | A kind of lithium ion battery cathode material and preparation method |
-
2020
- 2020-09-28 CN CN202011044506.4A patent/CN112242510A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2828202A1 (en) * | 2012-03-21 | 2015-01-28 | The Gillette Company | Methods of making metal-doped nickel oxide active materials |
| CN104659344A (en) * | 2015-01-30 | 2015-05-27 | 东南大学 | Lithium-site doped and metal oxide-coated lithium ion battery positive electrode material and preparation method thereof |
| CN104617253A (en) * | 2015-02-02 | 2015-05-13 | 吉林大学 | Method for preparing sulfur composite electrodes |
| CN106898775A (en) * | 2015-12-18 | 2017-06-27 | 国联汽车动力电池研究院有限责任公司 | Double cladded type richness lithium materials in a kind of surface and preparation method thereof |
| CN109256557A (en) * | 2018-10-23 | 2019-01-22 | 乳源东阳光磁性材料有限公司 | Nickelic layered oxide lithium electricity positive electrode of a kind of perofskite type oxide cladding and preparation method thereof |
| CN110783553A (en) * | 2019-11-26 | 2020-02-11 | 长虹格兰博科技股份有限公司 | A kind of lithium ion battery cathode material and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| KANGHUI HU等: "Na2S Treatment and Coherent Interface Modification of the Li-Rich Cathode to Address Capacity and Voltage Decay", 《APPLIED MATERIALS & INTERFACES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113113586A (en) * | 2021-04-07 | 2021-07-13 | 浙江大学 | Positive electrode for lithium ion battery and preparation method and application thereof |
| EP4318667A4 (en) * | 2021-08-25 | 2025-04-30 | SM Lab Co., Ltd. | Positive electrode active material, method for preparing same, and lithium secondary battery including positive electrode comprising same |
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