CN114335543A - Preparation method of organic matter supported lithium-rich manganese-based positive electrode material - Google Patents
Preparation method of organic matter supported lithium-rich manganese-based positive electrode material Download PDFInfo
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- CN114335543A CN114335543A CN202111681948.4A CN202111681948A CN114335543A CN 114335543 A CN114335543 A CN 114335543A CN 202111681948 A CN202111681948 A CN 202111681948A CN 114335543 A CN114335543 A CN 114335543A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 189
- 239000011572 manganese Substances 0.000 title claims abstract description 188
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 187
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 239000005416 organic matter Substances 0.000 title claims abstract description 86
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002105 nanoparticle Substances 0.000 claims abstract description 68
- 239000002245 particle Substances 0.000 claims abstract description 62
- 238000000576 coating method Methods 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 29
- 239000012756 surface treatment agent Substances 0.000 claims abstract description 15
- 238000004381 surface treatment Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 79
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 25
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 17
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 13
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229960001701 chloroform Drugs 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 12
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- -1 sulfenyl silane Chemical compound 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 229930192474 thiophene Natural products 0.000 claims description 8
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000010902 jet-milling Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 229920000767 polyaniline Polymers 0.000 abstract description 15
- 230000002776 aggregation Effects 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 239000004020 conductor Substances 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 14
- 239000010406 cathode material Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000010405 anode material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005056 compaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229920000123 polythiophene Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229920000128 polypyrrole Polymers 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 229940077388 benzenesulfonate Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- QJRVOJKLQNSNDB-UHFFFAOYSA-N 4-dodecan-3-ylbenzenesulfonic acid Chemical compound CCCCCCCCCC(CC)C1=CC=C(S(O)(=O)=O)C=C1 QJRVOJKLQNSNDB-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910003286 Ni-Mn Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
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- 230000001351 cycling effect Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
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- 238000006138 lithiation reaction Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 238000007709 nanocrystallization Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 229920000620 organic polymer Polymers 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
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- 150000004756 silanes Chemical class 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of an organic matter supported lithium-rich manganese-based positive electrode material, which comprises the steps of carrying out surface treatment on lithium-rich manganese-based micro-nano particles by using a surface treatment agent, carrying out organic matter coating treatment on the lithium-rich manganese-based micro-nano particles subjected to surface treatment by using a silane coupling agent, and then granulating the obtained organic matter coated mixed liquid to obtain the organic matter supported lithium-rich manganese-based positive electrode material; the preparation method can reduce the particle agglomeration phenomenon generated when the polyaniline is coated by the conductive material, can realize the in-situ compounding of the lithium-rich manganese base and the polyaniline, and improves the structural strength of the lithium-rich manganese base material.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a preparation method of an organic matter supported lithium-rich manganese-based positive electrode material.
Background
With the wide use of various electronic products and new energy electric vehicles, batteries of various materials have become a hot research topic and should be appliedIn the most widely used lithium ion batteries, the lithium-rich manganese-based positive electrode material is a potential positive electrode material for the next generation of lithium ion batteries due to the characteristics of high discharge specific capacity (2-4.8V exerts the specific capacity of more than 250 mAh/g), excellent cycle performance, low cost, environmental friendliness and the like. The molecular formula of the lithium-rich manganese-based cathode material is xLi2MnO3·(1-x)LiMO2Wherein M is a transition metal (Mn, Ni, Co, Ni-Mn, etc.). The lithium-rich manganese-based positive electrode material shows good cycling stability and high charge and discharge capacity in the charge and discharge processes, but the practical application of the lithium-rich manganese-based positive electrode material still has several problems: the first cycle irreversible capacity is as high as 40-100Ah/g, the rate capability is poor, and the 1C capacity is below 200 mAh/g; the high charging voltage causes decomposition of the electrolyte, so that the cycle performance is not ideal. In order to improve the electrochemical performance of the lithium-rich cathode material, search for a loose synthesis condition and solve the safety problem of the lithium ion battery, the material preparation is mainly improved at present. The electrochemical performance is generally improved by surface modification, bulk doping and particle nanocrystallization.
CN112234176A discloses a preparation method of an improved lithium-rich manganese-based material precursor, wherein the fluorine and magnesium co-doped lithium-rich manganese-based precursor is prepared by a binary system coprecipitation method, and magnesium ions and fluorine ions can be uniformly doped in the lithium-rich manganese-based material. The invention also provides the lithium-rich manganese-based precursor prepared by the preparation method, a lithium-rich manganese-based positive electrode material prepared from the lithium-rich manganese-based precursor and a lithium ion battery containing the positive electrode material. The lithium-rich manganese-based positive electrode material prepared by the preparation method can effectively improve the crystal stability of the material and inhibit voltage attenuation, and the prepared lithium ion battery has good electrochemical performance. And modifying the lithium-rich manganese-based positive electrode material. But because the fluorine-containing compound is used in the preparation process, the danger degree is high, and the environmental pollution is large.
CN113066971A discloses a gas phase coating method of a lithium-rich manganese-based positive electrode material, which comprises the following steps: A) placing the lithium-rich manganese-based positive electrode material and the polymer carbon material in the same container without contacting, and heating to pyrolyze the polymer carbon material in a protective gas atmosphere; B) and B), washing the material obtained in the step A) with water, and drying to obtain the lithium-rich manganese-based anode material coated by the organic carbon layer. According to the method, the surface of the lithium-rich manganese-based anode material is coated by adopting an organic polymer pyrolysis gas-phase product, and the organic carbon coating layer obtained by the method is extremely high in uniformity due to gas-solid contact, so that the problem of nonuniform coating in solid-solid coating can be effectively solved; the coated organic carbon layer can effectively inhibit the electrolyte from corroding the surface of the anode material, relieve the dissolution of transition metal ions such as Mn and the like on the surface of the material and inhibit the oxidative decomposition of the electrolyte; the coating layer is uniform and compact, the oxygen overflow in the first-round discharge process can be effectively inhibited, and the material cycle performance is improved. The method adopts the organic carbon layer for coating, so that the conductivity of the lithium-rich manganese-based positive electrode material is improved, but the electrode material particles coated by the organic carbon layer are easy to break, and the mechanical strength is not high.
CN108172759A discloses a polyaniline-coated ternary cathode material and a preparation method thereof, a battery cathode and a lithium battery, wherein the preparation method of the polyaniline-coated ternary cathode material comprises the following steps: and ball-milling and drying the mixture of the ternary cathode material, the polyaniline and the dispersant. The battery anode is prepared from the polyaniline-coated ternary anode material. This lithium cell, it includes: the positive electrode is prepared from the polyaniline-coated ternary positive electrode material. The coating of the ternary cathode material by the polyaniline is achieved by the mixture of the dispersing agent, the polyaniline and the ternary cathode material in a ball milling mode, so that the coating performance of the polyaniline on the material is better, the cycle performance of the battery can be improved, the electrochemical performance of the polyaniline can be better utilized, and the electrochemical performance of the ternary cathode material can be further improved. However, the method adopts ball milling to produce particles, the production efficiency is low, the particle structure is loose, the compaction of the conductive material and the coating layer is low, and the particles are fragile.
The improvement of the method for preparing the lithium-rich manganese-based material aiming at the conductivity and the structural strength has the defects of environmental pollution, poor effect and the like, and needs to be continuously improved on the basis of the prior art to solve the problems of poor conductivity, poor mechanical strength and the like.
Disclosure of Invention
Aiming at the problems of poor conductivity, fragile materials and the like of the lithium-rich manganese-based material in the prior art, the invention provides the preparation method of the organic matter supported lithium-rich manganese-based anode material, the preparation method reduces the particle aggregation phenomenon generated when the polyaniline is coated by the conductive material, solves the problems of poor conductivity and fragile materials of the lithium-rich manganese-based material through in-situ compounding, and improves the structural strength of the lithium-rich manganese-based material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of an organic-supported lithium-rich manganese-based positive electrode material, which comprises the following steps:
(1) carrying out surface treatment on the lithium-rich manganese-based micro-nano particles by using a surface treatment agent, and carrying out organic matter coating treatment on the lithium-rich manganese-based micro-nano particles subjected to surface treatment by using a silane coupling agent to obtain an organic matter coating mixed solution;
(2) granulating the organic matter coating mixed solution to obtain the organic matter supported lithium-rich manganese-based positive electrode material;
the organic matter in the organic matter coating treatment comprises any one or the combination of at least two of p-benzene, thiophene, pyrrole, styrene, acetylene or aniline.
According to the invention, the organic matter is coated to prepare the organic matter supported lithium-rich manganese-based cathode material, so that the problem of poor conductivity of the lithium-rich manganese-based material is solved, the overall conductivity is improved through the excellent conductivity of polyaniline, polyparaphenylene, polythiophene, polypyrrole, polystyrene or polyacetylene, the organic matter supporting material is beneficial to improving the high-voltage resistance of the lithium-rich manganese-based material, and the side reaction between the surface of the lithium-rich manganese-based material and electrolyte is reduced; through the treatment of the surface treating agent and the silane coupling agent, the agglomeration phenomenon in the coating process is effectively reduced, the homogeneity is improved, and the problem that the lithium-rich manganese-based material is fragile is solved; and (3) granulating the organic matter-coated mixed solution, and uniformly distributing conductive particles in the product by controlling the initial value of the lithium-rich manganese-based material and the median particle size of a finished product so as to obtain stable conductive performance.
In the invention, the organic matter in the organic matter supported lithium-rich manganese-based positive electrode material can be not limited to polyaniline, and can also be coated by poly (p-phenylene), polythiophene, polypyrrole, polystyrene or polyacetylene.
As a preferable technical scheme of the invention, the lithium-rich manganese-based micro-nano particles in the step (1) are obtained by crushing lithium-rich manganese-based particles.
Preferably, the lithium-rich manganese-based particles have a discharge capacity of 250-290mAh/g, such as 250-260 mAh/g, 270-280 mAh/g, or 290mAh/g, but not limited to the recited values, and other non-recited values within this range are equally applicable, preferably 260-280 mAh/g.
Preferably, the lithium-rich manganese-based particles have a median particle diameter of 3 to 4 μm, and may be, for example, 3 μm, 3.2 μm, 3.4 μm, 3.5 μm, 3.6 μm, 3.8 μm, or 4 μm, but are not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the lithium-rich manganese-based particles are preferably prepared using a carbonate. Preferably, sodium carbonate is used as a precipitator to prepare a lithium-rich manganese-based carbonate precipitate, and a lithium-rich manganese-based material is prepared by lithiation sintering, wherein the material prepared by the process has smaller primary particle size, looser particles and easy breakage, is beneficial to subsequent crushing, and is used for preparing nano particle slurry;
preferably, the method of comminution comprises jet milling.
Preferably, the lithium-rich manganese-based micro-nano particles have a median particle size of 0.1-1 μm, and may be, for example, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, or 1 μm, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferable technical scheme of the invention, the surface treatment in the step (1) comprises the steps of mixing the lithium-rich manganese-based micro-nano particles and the surface treating agent for the first time, carrying out solid-liquid separation, washing and drying.
Preferably, the surface treatment agent includes any one of ammonium sulfate, citric acid, or oxalic acid.
Ammonium sulfate, citric acid or oxalic acid is adopted for surface treatment, firstly, the surface of the nano particles is treated to form surface etching pits, and the surface is microscopically roughened, so that the coating stability of an organic phase is facilitated; secondly, further decomposing the micro-nano particles to decompose particle aggregate into single particles; the three materials are weak acid systems, which is beneficial to controlling the depth of surface treatment and avoiding excessive influence and damage on the matrix material.
Preferably, the concentration of the surface treatment agent is 0.001 to 0.1mol/L, and may be, for example, 0.001mol/L, 0.002mol/L, 0.005mol/L, 0.008mol/L, 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.08mol/L, or 0.1mol/L, but is not limited to the enumerated values, and other values within the numerical range are also applicable, and preferably 0.01 to 0.05 mol/L.
Preferably, the solid content of the mixture of the lithium-rich manganese-based micro-nano particles and the surface treatment agent in the first mixing is 5-60 wt%, for example, 5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt% or 60 wt%, but not limited to the recited values, and other values in the range are also applicable, preferably 20-50 wt%.
Preferably, the primary mixing comprises primary stirring.
Preferably, the time of the primary stirring is 1 to 300s, and may be, for example, 1s, 10s, 50s, 100s, 150s, 200s, 250s or 300s, but is not limited to the recited values, and other values not recited within the range of values are also applicable, preferably 50 to 200 s.
In a preferred embodiment of the present invention, the washing solution used for washing includes ethanol.
Preferably, the method of drying comprises flash evaporation.
As a preferred technical scheme of the present invention, the organic matter coating treatment in step (1) includes performing secondary mixing on the lithium-rich manganese-based micro-nano particles after surface treatment, a surfactant and a silane coupling agent to obtain the lithium-rich manganese-based nano slurry.
Preferably, the surfactant comprises a sulfonate and/or a phosphate salt.
Preferably, the mass ratio of the surfactant to the lithium-rich manganese-based micro-nano particles after drying is (0.001-0.5):1, and may be, for example, 0.001:1, 0.002:1, 0.005:1, 0.008:1, 0.01:1, 0.02:1 or 0.05:1, but is not limited to the enumerated values, and other non-enumerated values within the numerical range are also applicable, and are preferably (0.005-0.01): 1.
Preferably, the silane coupling agent includes any one or a combination of two or more of a vinyl silane, a sulfur-based silane, or an amino silane.
The lithium-rich manganese-based nano slurry is prepared by adopting the silane coupling agent, preferably the three silane coupling agents, and the silane coupling agent can be used as an elastic bridging agent between matrixes, so that the adhesion between materials with different chemical properties is improved, and the bonding strength between an organic support and the matrixes is enhanced. Preferably, the three silanes have a better bonding effect on the organic support, so that the bonding stability of the organic support is improved. The homogeneity of finished product particles is improved, and the particle agglomeration phenomenon is effectively inhibited.
Preferably, the mass ratio of the silane coupling agent to the dried lithium-rich manganese-based micro-nano particles is (0.1-1):1, and may be, for example, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1 or 1:1, but is not limited to the enumerated values, and other non-enumerated values within the numerical range are equally applicable, and are preferably (0.2-0.5): 1.
Preferably, in the second mixing, the solid content of the mixture of the lithium-rich manganese-based micro-nano particles, the surfactant and the silane coupling agent after drying is 60-80 wt%, preferably 65-75 wt%, and for example, may be 60 wt%, 62 wt%, 65 wt%, 68 wt%, 70 wt%, 72 wt%, 75 wt%, 78 wt% or 80 wt%, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
As a preferable technical solution of the present invention, the organic coating treatment in step (1) further includes: and mixing the lithium-rich manganese-based nano slurry and the organic matter solution for three times to obtain a three-time mixed material.
Preferably, the organic solution is prepared by dissolving organic matters in chloroform.
Preferably, the mass ratio of the organic substance to the trichloromethane is (1-5):1, and may be, for example, 1:1, 2:1, 3:1, 4:1 or 5:1, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, in the third mixing, the mass ratio of the organic substance to the lithium-rich manganese-based micro-nano particles is (0.01-0.1):1, and may be, for example, 0.01:1, 0.02:1, 0.05:1, 0.08:1 or 0.1:1, but is not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable.
Preferably, in the third mixing, the solid content of the mixture of the lithium-rich manganese-based nano-slurry and the organic solution is 10 to 40 wt%, preferably 20 to 30 wt%, and may be, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, or 40 wt%, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the organic matter in the organic matter coating treatment in step (1) includes any one or a combination of at least two of p-benzene, thiophene, pyrrole, styrene, acetylene or aniline.
As a preferable technical solution of the present invention, the organic coating treatment in step (1) further includes: and reacting the three-time mixed material after the three-time mixing with an iron-containing solution to obtain an organic matter-coated mixed solution.
Preferably, the reaction is stirred.
Preferably, the iron-containing solution comprises a ferric chloride solution.
Preferably, the concentration of ferric chloride in the iron-containing solution is 0.01-1 wt.%, preferably 0.05-0.5 wt.%, and may be, for example, 0.01 wt.%, 0.02 wt.%, 0.05 wt.%, 0.08 wt.%, 0.1 wt.%, 0.2 wt.%, 0.5 wt.%, 0.8 wt.%, or 1 wt.%, but is not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the reaction temperature is 30-70 ℃, preferably 40-60 ℃, for example 30 ℃, 40 ℃, 50 ℃, 60 ℃ or 70 ℃, but not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, the reaction time is 1-10min, preferably 4-8min, and may be, for example, 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
In a preferred embodiment of the present invention, the granulation method comprises spray granulation.
The traditional process adopts the step of directly drying organic matter slurry containing a lithium-rich manganese base to prepare the lithium-rich manganese base anode material, the lithium-rich manganese base and the organic matter are compounded in situ through spray granulation, and meanwhile, the invention limits the median particle size of lithium-rich manganese base raw material particles to be 0.1-1 mu m, so that the subsequent spray drying step is better matched, and the structural strength of the lithium-rich manganese base material is improved.
Preferably, the temperature of the spray granulation is from 100 ℃ to 300 ℃, preferably from 150 ℃ to 250 ℃, and may be, for example, 100 ℃, 150 ℃, 200 ℃, 250 ℃ or 300 ℃, but is not limited to the recited values, and other values not recited within the range are equally applicable.
Preferably, the organic-supported lithium-rich manganese-based positive electrode material has a median particle diameter of 3 to 15 μm, and may be, for example, 3 μm, 5 μm, 7 μm, 9 μm, 10 μm, 11 μm, 13 μm, or 15 μm, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
As a preferred embodiment of the present invention, the method comprises the steps of:
(1) the method comprises the steps of crushing lithium-rich manganese-based particles with the discharge capacity of 250-290mAh/g and the median particle size of 3-4 mu m by air flow to obtain lithium-rich manganese-based micro-nano particles with the median particle size of 0.1-1 mu m, mixing the lithium-rich manganese-based micro-nano particles and 0.001-0.1mol/L of a surface treating agent for the first time, filtering, washing and drying, mixing the dried lithium-rich manganese-based micro-nano particles, a surfactant and a silane coupling agent for the second time to obtain lithium-rich manganese-based nano slurry, mixing the lithium-rich manganese-based nano slurry and an organic matter solution for the third time, wherein the mass ratio of the organic matter to the lithium-rich manganese-based micro-nano particles is (0.01-0.1) and reacting with an iron-containing solution after mixing for the third time to obtain an organic matter coating mixed solution;
wherein the surface treatment agent comprises any one of ammonium sulfate, citric acid or oxalic acid, and the silane coupling agent comprises any one or the combination of more than two of vinyl silane, sulfenyl silane or amino silane;
(2) and carrying out spray granulation on the organic matter coating mixed solution at the temperature of 100-300 ℃ to obtain the organic matter supported lithium-rich manganese-based positive electrode material.
In a second aspect, the invention provides an organic-supported lithium-rich manganese-based positive electrode material obtained by the preparation method provided by the first aspect.
The conductivity of the organic matter supported lithium-rich manganese-based positive electrode material reaches 0.03-0.5 mu s/mm, and the powder compaction density is 2.2-2.7g/cm3And has good conductivity and structural strength.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method of the organic matter supported lithium-rich manganese-based cathode material, the surface treatment is carried out by adopting the surface treatment agent, the organic matter is coated by adopting the silane coupling agent, and the particle agglomeration phenomenon generated when the conductive material coats the organic matter is reduced;
(2) the preparation method of the organic matter supported lithium-rich manganese-based positive electrode material also forms the organic matter supported lithium-rich manganese-based material through spray drying, so that the lithium-rich manganese base and the organic matter are compounded in situ, the structural strength of the lithium-rich manganese-based material is improved, and the powder compaction density of a product prepared under the optimal condition is more than or equal to 2.46g/cm3The organic matter improves the whole conductivity by virtue of excellent conductivity, and the conductivity is more than or equal to 0.462 mu s/mm.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
It is to be understood that in the description of the present invention, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
The technical solution of the present invention is further explained by the following embodiments.
In one embodiment, the invention provides a preparation method of an organic-supported lithium-rich manganese-based positive electrode material, which comprises the following steps:
(1) the discharge capacity is 250-290mAh/g, and the lithium-rich manganese-based particles with the median particle size of 3-4 mu m are subjected to airflow crushing to obtain lithium-rich manganese-based micro-nano particles with the median particle size of 0.1-1 mu m; mixing the lithium-rich manganese-based micro-nano particles and a surface treating agent for the first time, filtering, washing and drying, mixing the dried lithium-rich manganese-based micro-nano particles, a surfactant and a silane coupling agent for the second time to obtain lithium-rich manganese-based nano slurry, mixing the lithium-rich manganese-based nano slurry and an organic solution for the third time, wherein a solvent of the organic solution is ferric trichloride, and reacting with the ferric trichloride after mixing for the third time to obtain an organic coating mixed solution;
wherein the surface treating agent comprises any one of ammonium sulfate, citric acid or oxalic acid, the concentration of the surface treating agent is 0.001-0.1mol/L, the solid content in the primary mixing is 5-60 wt%, and the stirring time of the primary mixing is 1-300 s; the silane coupling agent comprises any one or the combination of more than two of vinyl silane, sulfenyl silane or amino silane, the mass ratio of the surfactant to the silane coupling agent to the dried lithium-rich manganese-based micro-nano particles is (0.001-0.5): 0.1-1):1, and the solid content in the secondary mixing is 60-80 wt%; the mass ratio of the organic matter to the trichloromethane is (1-5):1, the mass ratio of the organic matter to the lithium-rich manganese-based micro-nano particles is (0.01-0.1):1, and the solid content in the three times of mixing is 10-40 wt%; the concentration of ferric trichloride is 0.01-1 wt%, the reaction temperature is 30-70 ℃, and the reaction time is 1-10 min;
(2) and carrying out spray granulation on the organic matter coating mixed solution at the temperature of 100-300 ℃ to obtain the organic matter supported lithium-rich manganese-based anode material with the median particle size of 3-15 mu m.
It is understood that processes or substitutions and variations of conventional data provided by embodiments of the present invention are within the scope and disclosure of the present invention.
Example 1
The embodiment provides a preparation method of an organic matter supported lithium-rich manganese-based positive electrode material, which comprises the following steps:
(1) lithium-rich manganese-based particles with discharge capacity of 270mAh/g and median particle size of 3.5 mu m are subjected to airflow crushing to obtain lithium-rich manganese-based micro-nano particles with median particle size of 0.5 mu m; the lithium-rich manganese-based micro-nano particles and ammonium sulfate (NH)4)2SO4Mixing, filtering, washing and drying the mixture for the first time, mixing the dried lithium-rich manganese-based micro-nano particles, sulfonate linear alkyl benzene sulfonic acid sodium LAS (CAS:25155-30-0) and vinyl silane for the second time to obtain lithium-rich manganese-based nano slurry, mixing the lithium-rich manganese-based nano slurry and an aniline solution for the third time, wherein the solvent of the aniline solution is trichloromethane CHCl3Mixing the mixture for the third time and then reacting the mixture with ferric trichloride to obtain organic matter coated mixed liquor;
wherein the concentration of the ammonium sulfate is 0.01mol/L, the solid content in the primary mixing is 30 wt%, and the stirring time of the primary mixing is 150 s; the mass ratio of the sulfonate to the vinyl silane to the dried lithium-rich manganese-based micro-nano particles is 0.008:0.3:1, and the solid content in the secondary mixing is 70 wt%; the mass ratio of aniline to trichloromethane is 3:1, and aniline (C)6H7N, CAS: 62-53-3) and the lithium-rich manganese-based micro-nano particles are mixed at a mass ratio of 0.05:1, and the solid content in the three times of mixing is 25 wt%; the concentration of ferric trichloride is 0.1 wt%, the reaction temperature is 50 ℃, and the reaction time is 6 min;
(2) and carrying out spray granulation on the organic matter coating mixed solution at 200 ℃ to obtain the organic matter supported lithium-rich manganese-based positive electrode material with the median particle size of 10 micrometers.
Example 2
The embodiment provides a preparation method of an organic matter supported lithium-rich manganese-based positive electrode material, which comprises the following steps:
(1) carrying out air flow crushing on the lithium-rich manganese-based particles with the discharge capacity of 250mAh/g and the median particle size of 3 mu m to obtain lithium-rich manganese-based micro-nano particles with the median particle size of 0.1 mu m; mixing the lithium-rich manganese-based micro-nano particles and citric acid for the first time, filtering, washing and drying, mixing the dried lithium-rich manganese-based micro-nano particles, phosphate ester lauryl alcohol potassium phosphate (CAS: 58318092-6) and sulfenyl silane for the second time to obtain lithium-rich manganese-based nano slurry, mixing the lithium-rich manganese-based nano slurry and an aniline solution for the third time, wherein a solvent of the aniline solution is ferric trichloride, and reacting the mixture with the ferric trichloride after the third mixing to obtain an organic matter coating mixed solution;
wherein the concentration of the citric acid is 0.001-0.1mol/L, the solid content in the primary mixing is 5-60 wt%, and the stirring time of the primary mixing is 10 s; the mass ratio of the phosphate salt to the sulfenyl silane to the dried lithium-rich manganese-based micro-nano particles is 0.001:1:1, and the solid content in the secondary mixing is 60 wt%; the mass ratio of the aniline to the trichloromethane is 5:1, the mass ratio of the aniline to the lithium-rich manganese-based micro-nano particles is 0.1:1, and the solid content in the three times of mixing is 10 wt%; the concentration of ferric trichloride is 0.01 wt%, the reaction temperature is 70 ℃, and the reaction time is 1 min;
(2) and carrying out spray granulation on the organic matter coating mixed solution at 300 ℃ to obtain the organic matter supported lithium-rich manganese-based positive electrode material with the median particle size of 3 mu m.
Example 3
The embodiment provides a preparation method of an organic matter supported lithium-rich manganese-based positive electrode material, which comprises the following steps:
(1) carrying out air flow crushing on the lithium-rich manganese-based particles with the discharge capacity of 290mAh/g and the median particle size of 4 mu m to obtain lithium-rich manganese-based micro-nano particles with the median particle size of 1 mu m; mixing, filtering, washing and drying the lithium-rich manganese-based micro-nano particles and oxalic acid at one time, wherein the dried lithium-rich manganese-based micro-nano particles and the sulfonated substance are as follows: sodium Linear alkyl benzene sulfonate LAS (CAS:25155-30-0) and aminosilane: aminopropyl triethoxysilane (CAS: 5089-72-5), performing secondary mixing to obtain lithium-manganese-based nano slurry, performing tertiary mixing on the lithium-manganese-based nano slurry and an aniline solution, wherein a solvent of the aniline solution is ferric chloride, and reacting the aniline solution with ferric chloride after the tertiary mixing to obtain an organic matter coating mixed solution;
wherein, the concentration of oxalic acid is 0.1mol/L, the solid content in the first mixing is 60 wt%, and the stirring time of the first mixing is 300 s; the mass ratio of the sulfonate to the aminosilane to the dried lithium-rich manganese-based micro-nano particles is 0.5:0.1:1, and the solid content in the secondary mixing is 80 wt%; the mass ratio of the aniline to the trichloromethane is 1:1, the mass ratio of the aniline to the lithium-rich manganese-based micro-nano particles is 0.1:1, and the solid content in the three times of mixing is 40 wt%; the concentration of ferric trichloride is 1 wt%, the reaction temperature is 30 ℃, and the reaction time is 10 min;
(2) and carrying out spray granulation on the organic matter coating mixed solution at 100 ℃ to obtain the organic matter supported lithium-rich manganese-based positive electrode material with the median particle size of 15 micrometers.
Example 4
The method is basically the same as the method provided in example 1, except that the lithium-rich manganese-based micro-nano particles and sulfuric acid are subjected to primary mixing, filtering, washing and drying.
Example 5
The method is basically the same as the method provided in example 1, except that the silane coupling agent mixed with the dried lithium-rich manganese-based micro-nano particles is epoxy silane: glycidoxypropyltrimethoxysilane (CAS: 2530-83-8).
Example 6
The process was essentially the same as that provided in example 1, except that the organic-coated mixed liquor was dried at 200 ℃ under a nitrogen atmosphere.
Example 7
The embodiment provides a preparation method of an organic matter supported lithium-rich manganese-based positive electrode material, which comprises the following steps:
(1) the lithium-rich manganese-based particles with the discharge capacity of 270mAh/g and the median particle size of 3.5 mu m are subjected to air flow crushing to obtain the median particle size of 0.5 mu m of lithium-rich manganese-based micro-nano particles; the lithium-rich manganese-based micro-nano particles and ammonium sulfate (NH)4)2SO4Mixing, filtering, washing and drying the mixture for the first time, mixing the dried lithium-rich manganese-based micro-nano particles, sulfonate linear alkyl benzene sulfonate LAS (CAS:25155-30-0) and vinyl silane for the second time to obtain lithium-rich manganese-based nano slurry, mixing the lithium-rich manganese-based nano slurry and a pyrole solution for the third time, wherein the solvent of the pyrole solution is trichloromethane CHCl3After the three times of mixing, the mixture reacts with ferric trichloride to obtain polypyrrole coating mixed liquor;
wherein the concentration of the ammonium sulfate is 0.01mol/L, the solid content in the primary mixing is 30 wt%, and the stirring time of the primary mixing is 150 s; the mass ratio of the sulfonate to the vinyl silane to the dried lithium-rich manganese-based micro-nano particles is 0.008:0.3:1, and the solid content in the secondary mixing is 70 wt%; the mass ratio of arsenicum and trichloromethane is 3:1, arsenicum (C)4H5N, CAS: 62-53-3) and the lithium-rich manganese-based micro-nano particles are mixed at a mass ratio of 0.05:1, and the solid content in the three times of mixing is 25 wt%; the concentration of ferric trichloride is 0.1 wt%, the reaction temperature is 50 ℃, and the reaction time is 6 min;
(2) and spraying and granulating the polypyrrole-coated mixed solution at 200 ℃ to obtain the polypyrrole-supported lithium-rich manganese-based positive electrode material with the median particle size of 10 mu m.
Example 8
The embodiment provides a preparation method of an organic matter supported lithium-rich manganese-based positive electrode material, which comprises the following steps:
(1) lithium-rich manganese-based particles with discharge capacity of 270mAh/g and median particle size of 3.5 mu m are subjected to airflow crushing to obtain lithium-rich manganese-based micro-nano particles with median particle size of 0.5 mu m; the lithium-rich manganese-based micro-nano particles and ammonium sulfate (NH)4)2SO4Mixing, filtering, washing and drying the mixture for the first time, mixing the dried lithium-rich manganese-based micro-nano particles, sulfonate linear alkyl benzene sulfonate LAS (CAS:25155-30-0) and vinyl silane for the second time to obtain lithium-rich manganese-based nano slurry, mixing the lithium-rich manganese-based nano slurry and a thiophene solution for the third time, wherein the solvent of the thiophene solution is trichloro chlorideMethane CHCl3After the three times of mixing, reacting with ferric trichloride to obtain a polythiophene coated mixed solution;
wherein the concentration of the ammonium sulfate is 0.01mol/L, the solid content in the primary mixing is 30 wt%, and the stirring time of the primary mixing is 150 s; the mass ratio of the sulfonate to the vinyl silane to the dried lithium-rich manganese-based micro-nano particles is 0.008:0.3:1, and the solid content in the secondary mixing is 70 wt%; the mass ratio of the thiophene to the trichloromethane is 3:1, and the thiophene (C)4H4S, CAS: 110-02-1) and the lithium-rich manganese-based micro-nano particles in a mass ratio of 0.05:1, wherein the solid content in the three times of mixing is 25 wt%; the concentration of ferric trichloride is 0.1 wt%, the reaction temperature is 50 ℃, and the reaction time is 6 min;
(2) and carrying out spray granulation on the polythiophene coated mixed solution at 200 ℃ to obtain the polythiophene supported lithium-rich manganese-based positive electrode material with the median particle size of 10 microns.
Comparative example 1
The method is basically the same as the method provided in example 1, except that the lithium-rich manganese-based micro-nano particles are not mixed for one time.
Comparative example 2
Essentially the same procedure as provided in example 1, except that no alkane coupling agent was added to the second mixing.
Comparative example 3
Basically the same as the method provided in example 1, except that polyethylene is used for coating treatment, and finally the polyethylene-supported lithium-rich manganese-based cathode material is obtained.
Comparative example 4
Substantially the same method as provided in example 1, except that three times of mixing and reaction were not performed, a lithium-rich manganese-based positive electrode material without a coating layer was obtained.
The positive electrode materials obtained in examples 1 to 8 and comparative examples 1 to 4 were subjected to a powder conductivity meter (FT-8100, rekoku brand), conductivity was measured according to the test methods of standard GB/T1551, GB/T1552-1995, and powder compaction density was measured according to the test methods of GB/T2433and 2009, and the test results are shown in table 1.
TABLE 1
From the data in Table 1 we can see that:
(1) the organic matter supported lithium-rich manganese-based positive electrode material obtained by the method of the embodiment 1-3 has good conductivity, the conductivity is more than or equal to 0.462 mu s/mm, the structural strength is higher, and the powder compaction density is more than or equal to 2.46g/cm3Therefore, the preparation method of the organic matter supported lithium-rich manganese-based cathode material provided by the invention reduces the particle agglomeration phenomenon generated by organic matter coating and improves the product quality;
(2) it can be seen from the combination of examples 1 and 4-5 that in examples 4 and 5, compared with example 1, the organic supported lithium-rich manganese-based cathode material obtained by using sulfuric acid as a surface treatment agent and glycidoxypropyltrimethoxysilane as a silane coupling agent respectively has the electrical conductivity of only 0.082 mu s/mm and 0.048 mu s/mm and the powder compaction density of 2.40g/cm3And 2.41g/cm3While example 1 used ammonium sulfate as a surface treatment agent and vinyl silane as a silane coupling agent, the product had an electrical conductivity of 0.498. mu.s/mm and a powder compacted density of 2.68g/cm3Therefore, the invention adopts the surface treating agent and the silane coupling agent of the preferred types to obtain the organic matter supported lithium-rich manganese-based anode material with good conductive effect and stable surface and internal properties;
(3) it can be seen from the combination of example 1 and example 6 that in example 6, compared with example 1, the spray drying step is omitted, only heating drying is used, and the conductivity of the organic-supported lithium-rich manganese-based positive electrode material obtained in example 6 is only 0.007 mus/mm, and the powder compacted density is 1.93g/cm3(ii) a Whereas example 1 used spray drying, the product had an electrical conductivity of 0.498. mu.s/mm and a powder compacted density of 2.68g/cm3Therefore, the method for spray drying is adopted, the powder performance is optimized, and the obtained organic matter supported lithium-rich manganese-based anode material is stable in surface property and high in conductivity;
(4) it can be seen from the combination of example 1 and examples 7-8 that, in example 7 and example 8, compared with example 1, example 7 was coated with polypyrrole and example 8 was coated with polythiophene, the conductivity of the organic-supported lithium-rich manganese-based positive electrode materials obtained in examples 7 and 8 was 0.559 μ s/mm and 0.517 μ s/mm, respectively, and the powder compaction densities were 2.43g/cm3And 2.56g/cm3(ii) a Whereas example 1 used spray drying, the product had an electrical conductivity of 0.498. mu.s/mm and a powder compacted density of 2.68g/cm3Therefore, the coating organic matter of the lithium-rich manganese-based material can adopt not only the principal component but also other organic matters in the optimal range, and the performance of the obtained product is equivalent to that of a phenol coating method;
(5) it can be seen from the combination of example 1 and comparative examples 1 to 4 that comparative example 1 omitted the step of mixing once compared with example 1, comparative example 2 did not add a silane coupling agent compared with example 1, comparative example 3 was coated and supported with polyethylene compared with example 1, and comparative example 4 omitted three times of mixing and reaction compared with example 1, to obtain a product without a coating layer, and the obtained organic-supported lithium-rich manganese-based positive electrode material had an electric conductivity of only 0.005. mu.s/mm, 0.004. mu.s/mm, 0.005. mu.s/mm and 0.002. mu.s/mm, and a powder compacted density of only 2.28g/cm3、2.03g/cm3、1.84g/cm3And 1.71g/cm3Therefore, the powder surface and internal performance of the organic matter supported lithium-rich manganese-based anode material prepared by the scheme of the invention is good, and the obtained organic matter supported lithium-rich manganese-based anode material has high conductivity.
In summary, according to the organic matter supported lithium-rich manganese-based positive electrode material and the preparation method thereof provided by the invention, the preferable surface treating agent and silane coupling agent are adopted, the occurrence of particle agglomeration phenomenon generated when the polyaniline is coated by the conductive material is reduced, the overall conductivity is improved by virtue of excellent conductivity, and the process method is suitable for industrial production.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the organic matter supported lithium-rich manganese-based positive electrode material is characterized by comprising the following steps of:
(1) carrying out surface treatment on the lithium-rich manganese-based micro-nano particles by using a surface treatment agent, and carrying out organic matter coating treatment on the lithium-rich manganese-based micro-nano particles subjected to surface treatment by using a silane coupling agent to obtain an organic matter coating mixed solution;
(2) granulating the organic matter coating mixed solution to obtain the organic matter supported lithium-rich manganese-based positive electrode material;
the organic matter in the organic matter coating treatment comprises any one or the combination of at least two of p-benzene, thiophene, pyrrole, styrene, acetylene or aniline.
2. The preparation method according to claim 1, wherein the lithium-rich manganese-based micro-nano particles in step (1) are obtained by crushing lithium-rich manganese-based particles;
preferably, the discharge capacity of the lithium-rich manganese-based particles is 250-290mAh/g, preferably 260-280 mAh/g;
preferably, the lithium-rich manganese-based particles have a median particle size of 3 to 4 μm;
preferably, the method of comminution comprises jet milling;
preferably, the lithium-rich manganese-based micro-nano particles have a median particle size of 0.1-1 μm.
3. The preparation method according to claim 1 or 2, wherein the surface treatment in the step (1) comprises mixing the lithium-rich manganese-based micro-nano particles and the surface treatment agent at one time, performing solid-liquid separation, washing and drying;
preferably, the surface treatment agent includes any one of ammonium sulfate, citric acid, or oxalic acid;
preferably, the concentration of the surface treatment agent is 0.001-0.1mol/L, preferably 0.01-0.05 mol/L;
preferably, in the primary mixing, the solid content of the mixture of the lithium-rich manganese-based micro-nano particles and the surface treatment agent is 5-60 wt%, and preferably 20-50 wt%;
preferably, the primary mixing comprises primary stirring;
preferably, the time of the one-time stirring is 1 to 300s, preferably 50 to 200 s.
4. The production method according to claim 3, wherein the washing solution used for the washing comprises ethanol;
preferably, the method of drying comprises flash evaporation.
5. The preparation method according to any one of claims 1 to 4, wherein the organic matter coating treatment in step (1) comprises performing secondary mixing on the lithium-rich manganese-based micro-nano particles subjected to surface treatment, a surfactant and a silane coupling agent to obtain lithium-rich manganese-based nano slurry;
preferably, the surfactant comprises a sulfonate and/or a phosphate salt;
preferably, the mass ratio of the surfactant to the dried lithium-rich manganese-based micro-nano particles is (0.001-0.5):1, preferably (0.005-0.01): 1;
preferably, the silane coupling agent comprises any one or a combination of two or more of vinyl silane, sulfur-based silane or amino silane;
preferably, the mass ratio of the silane coupling agent to the dried lithium-rich manganese-based micro-nano particles is (0.1-1):1, preferably (0.2-0.5): 1;
preferably, in the secondary mixing, the solid content of the mixture of the dried lithium-rich manganese-based micro-nano particles, the surfactant and the silane coupling agent is 60-80 wt%, and preferably 65-75 wt%.
6. The method according to claim 5, wherein the organic coating treatment in the step (1) further comprises: mixing the lithium-rich manganese-based nano slurry and the organic matter solution for three times to obtain a third mixed material;
preferably, the organic solution is prepared by dissolving organic matters in chloroform;
preferably, the mass ratio of the organic matter to the trichloromethane is (1-5) to 1;
preferably, in the third mixing, the mass ratio of the organic matter to the lithium-rich manganese-based micro-nano particles is (0.01-0.1): 1;
preferably, in the third mixing, the solid content of the mixture of the lithium-rich manganese-based nano slurry and the organic solution is 10-40 wt%, preferably 20-30 wt%;
preferably, the organic matter in the organic matter coating treatment in step (1) includes any one or a combination of at least two of p-benzene, thiophene, pyrrole, styrene, acetylene or aniline.
7. The method according to claim 6, wherein the organic coating treatment in the step (1) further comprises: reacting the three-time mixed material after the three-time mixing with an iron-containing solution to obtain an organic matter-coated mixed solution;
preferably, the reaction is stirred;
preferably, the iron-containing solution comprises a ferric chloride solution;
preferably, the concentration of ferric trichloride in the iron-containing solution is 0.01 to 1 wt%, preferably 0.05 to 0.5 wt%;
preferably, the temperature of the reaction is 30-70 ℃, preferably 40-60 ℃;
preferably, the reaction time is 1-10min, preferably 4-8 min.
8. The production method according to any one of claims 1 to 7, wherein the granulation in step (2) comprises spray granulation;
preferably, the temperature of the spray granulation is 100-300 ℃, preferably 150-250 ℃;
preferably, the organic matter-supported lithium-rich manganese-based positive electrode material has a median particle diameter of 3 to 15 μm.
9. The method for preparing according to any one of claims 1 to 8, characterized in that it comprises the steps of:
(1) the method comprises the steps of crushing lithium-rich manganese-based particles with the discharge capacity of 250-290mAh/g and the median particle size of 3-4 mu m by air flow to obtain lithium-rich manganese-based micro-nano particles with the median particle size of 0.1-1 mu m, mixing the lithium-rich manganese-based micro-nano particles and 0.001-0.1mol/L of a surface treating agent for the first time, filtering, washing and drying, mixing the dried lithium-rich manganese-based micro-nano particles, a surfactant and a silane coupling agent for the second time to obtain lithium-rich manganese-based nano slurry, mixing the lithium-rich manganese-based nano slurry and an organic matter solution for the third time, wherein the mass ratio of the organic matter to the lithium-rich manganese-based micro-nano particles is (0.01-0.1) and reacting with an iron-containing solution after mixing for the third time to obtain an organic matter coating mixed solution;
wherein the surface treatment agent comprises any one of ammonium sulfate, citric acid or oxalic acid, and the silane coupling agent comprises any one or the combination of more than two of vinyl silane, sulfenyl silane or amino silane;
(2) and carrying out spray granulation on the organic matter coating mixed solution at the temperature of 100-300 ℃ to obtain the organic matter supported lithium-rich manganese-based positive electrode material.
10. An organic-supported lithium-rich manganese-based positive electrode material, which is obtained by the production method according to any one of claims 1 to 9.
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