CN116750810A - Single-crystal type high-nickel ternary positive electrode material for high-voltage lithium ion battery and preparation method thereof - Google Patents
Single-crystal type high-nickel ternary positive electrode material for high-voltage lithium ion battery and preparation method thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 106
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000013078 crystal Substances 0.000 title claims abstract description 49
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 118
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 37
- 238000005406 washing Methods 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 96
- 238000000227 grinding Methods 0.000 claims description 74
- 238000003756 stirring Methods 0.000 claims description 68
- 238000001354 calcination Methods 0.000 claims description 49
- 229910052760 oxygen Inorganic materials 0.000 claims description 48
- 238000007873 sieving Methods 0.000 claims description 47
- 239000012298 atmosphere Substances 0.000 claims description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 46
- 239000008367 deionised water Substances 0.000 claims description 46
- 229910021641 deionized water Inorganic materials 0.000 claims description 46
- 239000001301 oxygen Substances 0.000 claims description 46
- 238000001816 cooling Methods 0.000 claims description 44
- 239000002243 precursor Substances 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 28
- 239000012065 filter cake Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 239000004570 mortar (masonry) Substances 0.000 claims description 25
- 238000001291 vacuum drying Methods 0.000 claims description 23
- 238000000967 suction filtration Methods 0.000 claims description 22
- 229910052593 corundum Inorganic materials 0.000 claims description 20
- 239000010431 corundum Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 17
- 238000005245 sintering Methods 0.000 abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 11
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 abstract description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 abstract description 5
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000006138 lithiation reaction Methods 0.000 abstract description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract description 4
- 230000005496 eutectics Effects 0.000 abstract description 3
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 3
- 159000000002 lithium salts Chemical class 0.000 abstract description 3
- 239000002341 toxic gas Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 133
- 239000000843 powder Substances 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 29
- 239000007788 liquid Substances 0.000 description 24
- 229910013716 LiNi Inorganic materials 0.000 description 23
- 238000005303 weighing Methods 0.000 description 23
- 239000010406 cathode material Substances 0.000 description 14
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 9
- 230000001351 cycling effect Effects 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a monocrystal type high-nickel ternary anode material for a high-voltage lithium ion battery, which is characterized in that a binary fluxing agent is constructed by lithium hydroxide and lithium carbonate, the minimum eutectic temperature is about 418.2 ℃, and on one hand, the uniformity and the reaction rate of lithiation reaction are improved; on the other hand, the sintering temperature is reduced, and the specific capacity and the sintering morphology of the material are improved; meanwhile, the excessive lithium source obtained by selecting the two lithium salts as fluxing agents can inhibit unstable Ni 3+ Is reduced at high temperature, reduces the phenomenon of mixed discharge of lithium and nickel, and avoids the productionSintering with lithium sulfate, lithium chloride, and lithium nitrate results in toxic gases (SO 2 、NO 2 And Cl 2 Etc.), the single-crystal high-nickel ternary positive electrode material prepared by the subsequent steps of sectional high-temperature primary sintering, water washing and high-temperature secondary sintering has uniform particle size and good dispersibility, and shows good comprehensive electrochemical performance in high-voltage electrolyte.
Description
Technical field:
the invention relates to a monocrystal type high-nickel ternary positive electrode material for a high-voltage lithium ion battery and a preparation method thereof.
The background technology is as follows:
the lithium ion battery has the advantages of high energy density, high working voltage, small volume and the like, and is widely applied to the fields of mobile communication equipment, small electronic products, new energy automobiles and the like. With the continuous improvement of the demands of people, the consumer market has higher requirements on the comprehensive performances of the lithium ion battery, such as capacity, cycle life, safety and the like. Meanwhile, under the background of global carbon peak and carbon neutralization, the high requirements of new energy markets on the continuous voyage of electric automobiles force the lithium ion power battery anode material to develop to a high-energy density material, so that the single crystallization of the high-nickel anode material becomes the trend of the future lithium battery anode material development. The high-nickel ternary positive electrode material is made into a single crystal morphology, so that the positive electrode material has larger primary particles and lower specific surface area, lattice distortion generated in the high-voltage charge-discharge process of the material can be effectively inhibited, side reaction between the surface of the positive electrode material and electrolyte is reduced, and excellent electrochemical performance is realized.
The monocrystal type high-nickel ternary anode material has good thermal stability and structural stability. Mainly because the material particles have no grain boundary inside, the inter-crystal cracks generated by anisotropic shrinkage and expansion of the lithium intercalation and deintercalation active substance particles in the electrochemical process are radically eliminated, thereby inhibiting the structural collapse of the material and the side reaction inside the crystal grains in the charge and discharge process. Compared with the high-nickel polycrystalline material, single crystal particles of the single crystal high-nickel material have better structural integrity than loosely aggregated polycrystalline particles, and can reach higher tap density in the pressing process of the pole piece to realize higher volume energy density; the expansion/contraction of the lattice volume of the monocrystal material in the lithium intercalation and deintercalation process is isotropic, so that the risk of microcrack generation in the circulation process can be greatly reduced; the monocrystal particles have smaller specific surface area and good dispersibility, can be better contacted with the conductive agent, and are beneficial to the transmission of lithium ions.
The high-temperature solid phase method and the molten salt auxiliary method are the main methods for synthesizing the single crystal cathode material at present. The molten salt auxiliary method is used for reducing the calcination temperature, and auxiliary agents such as fluxing agent, pore-forming agent, crystal face modifier and the like are added into the precursor in the process of preparing the monocrystal to sinter and synthesize the monocrystal anode material. The fluxing agent is typically one or more low melting salts. The method mainly uses the cosolvent to convert the lithiated solid-solid reaction into the solid-liquid reaction, so that the reactants can realize the atomic/molecular scale mixing in the liquid phase, thereby accelerating the diffusion rate of ions, shortening the reaction time and reducing the reaction temperature.
CN110923801B discloses a preparation method and application of single crystal ternary material. The method comprises the steps of firstly preparing a monocrystal precursor, adding a fluxing agent in the process of preparing the precursor, and preparing a monocrystal ternary material after lithium matching. The traditional one-step synthesis method is disassembled into two steps of synthesis of a monocrystal precursor and lithium-matching roasting, compared with the one-step lithiation monocrystal process, the Li/Ni mixed discharge is reduced, and the capacity and the first effect of the monocrystal ternary material are improved. The fluxing agent is a two-phase composite fluxing agent B 2 O 3 +Bi 2 O 3 、ZrO 2 +B 2 O 3 、Al 2 O 3 +B 2 O 3 、LiF+AlF、KCl+MgCl 2 Or three-phase composite fluxing agents LiF+NaF+KF, liF+AlF+CsF and KF+LiF+CsF.
CN115172719a discloses a preparation method of a high-voltage monocrystal ternary material. The grain boundary fusion energy is reduced by means of a low-melting-point fluxing agent, the directional microcrystal nucleus is obtained by presintering at low temperature, the directional microcrystal nucleus reacts with a structure stabilizer at high temperature to realize the directional growth of the crystal nucleus, the directional growth of the crystal grains is realized, meanwhile, the material has higher compaction density, and the capacity, the high-low temperature circulation and the multiplying power performance of the material are obviously superior to those of the traditional monocrystal ternary anode material. The selected fluxing agent is one or more of boron oxide, boric acid, boron chloride and boron fluoride.
CN114703545a discloses a method for preparing high-capacity monocrystal ternary cathode material by infiltration dispersion method, which effectively reduces the synthesis temperature of monocrystal ternary cathode material, and the prepared submicron-level material has the advantages of good morphology, good uniformity of particle size and the like. The molten salt is one or the combination of more than two of lithium oxide, lithium peroxide, lithium hydroxide, lithium acetate, lithium chloride, lithium nitrate and lithium sulfate.
The above patent applications all use molten salt assisted method to prepare single crystal ternary materials. The material particles obtained by selecting different molten salt systems still have a certain agglomeration phenomenon, so that the exerted technical effects have a certain difference.
The invention comprises the following steps:
the invention aims to provide a preparation method of a monocrystal type high-nickel ternary positive electrode material for a high-voltage lithium ion battery, which is characterized in that a binary fluxing agent is constructed by lithium hydroxide and lithium carbonate, the minimum eutectic temperature is about 418.2 ℃, and on one hand, the uniformity and the reaction rate of lithiation reaction are improved; on the other hand, the sintering temperature is reduced, and the specific capacity and the sintering morphology of the material are improved; meanwhile, the excessive lithium source obtained by selecting the two lithium salts as fluxing agents can inhibit unstable Ni 3+ Is reduced at high temperature, reduces the mixed discharge of lithium and nickel, and avoids toxic gas (SO) caused by sintering process of lithium sulfate, lithium chloride and lithium nitrate 2 、NO 2 And Cl 2 Etc.), the single-crystal high-nickel ternary positive electrode material prepared by the subsequent steps of sectional high-temperature primary sintering, water washing and high-temperature secondary sintering has uniform particle size and good dispersibility, and shows good comprehensive electrochemical performance in high-voltage electrolyte.
The invention is realized by the following technical scheme:
the preparation method of the monocrystal type high-nickel ternary positive electrode material for the high-voltage lithium ion battery comprises the following steps of:
1) Ni is added with 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor and LiOH H 2 O、Li 2 CO 3 Grinding in a mortar, and mixing uniformly; wherein LiOH.H 2 O and Li 2 CO 3 Constructing a binary fluxing agent, wherein the total mole percentage of the fluxing agent is 100%, and LiOH.H in a cosolvent 2 The mole fraction of O is: 74% -84%, the rest is Li 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the Li and Ni in flux 0.88 Co 0.09 Mn 0.03 (OH) 2 The molar ratio of the sum of all metal atoms of the precursor (Li/Me, me=Ni+Co+Mn) is (1.15-2): 1; preferably (1.6-1.9): 1;
2) Placing the uniformly mixed material obtained in the step 1) in an oxygen atmosphere for sectional calcination, firstly heating to 400-600 ℃ at a heating rate of 3-5 ℃/min for 2-6 h, then heating to 750 ℃ for 5-15 h, continuously heating to 800-900 ℃ for 5-15 h, finally cooling to room temperature along with a furnace, crushing and grinding, and sieving with a 300-mesh sieve to obtain a ternary anode material;
3) Mixing the material obtained in the step 2) with deionized water, stirring for 20-40 min at a feed-liquid ratio of 1:20-1:30, standing until the solution is completely layered, pouring out the upper layer solution, adding deionized water, repeatedly washing for 3 times until the pH value is no longer reduced, carrying out suction filtration, putting the filter cake into a vacuum drying box, drying for 20-28 h at 70-90 ℃, putting the filter cake into a corundum crucible again, calcining for 4-8 h at 600-850 ℃ preferably 700-750 ℃ in an oxygen atmosphere, cooling to room temperature along with a furnace, grinding and screening, and obtaining the single crystal type high nickel ternary positive electrode material for the high voltage lithium ion battery.
The beneficial effects of the invention are as follows:
according to the invention, the binary fluxing agent is constructed by lithium hydroxide and lithium carbonate, the minimum eutectic temperature of the two is about 418.2 ℃, on one hand, precursor solutes are dissolved in molten salt, and the uniformity and the reaction rate of lithiation reaction are improved; on the other hand, the sintering temperature is reduced, and the specific capacity and the sintering morphology of the material are improved; meanwhile, the excessive lithium source obtained by selecting the two lithium salts as fluxing agents can inhibit unstable Ni 3+ Is reduced at high temperature, reduces the mixed discharge of lithium and nickel, and avoids toxic gas (SO) caused by sintering process of lithium sulfate, lithium chloride and lithium nitrate 2 、NO 2 And Cl 2 Etc.), the single-crystal high-nickel ternary positive electrode material prepared by the subsequent steps of sectional high-temperature primary sintering, water washing and high-temperature secondary sintering has uniform particle size and good dispersibility, and shows good comprehensive electrochemical performance in high-voltage electrolyte.
Description of the drawings:
fig. 1 is an SEM image of a single-crystal type high-nickel ternary cathode material for a high-voltage lithium ion battery obtained in example 3.
Fig. 2 is an SEM image of the single-crystal type high-nickel ternary cathode material for a high-voltage lithium ion battery obtained in example 4.
Fig. 3 is an SEM image of the single-crystal type high-nickel ternary cathode material for a high-voltage lithium ion battery obtained in example 7.
Fig. 4 is an SEM image of the single-crystal high-nickel ternary cathode material for a high-voltage lithium ion battery obtained in example 8.
Fig. 5 is an SEM image of the single-crystal high-nickel ternary cathode material for a high-voltage lithium ion battery obtained in example 11.
Fig. 6 is an SEM image of a single-crystal type high-nickel ternary cathode material for a high-voltage lithium ion battery obtained in example 13.
Fig. 7 is an SEM image of the ternary cathode material obtained in comparative example 1.
Fig. 8 is an SEM image of the ternary cathode material obtained in comparative example 7.
Fig. 9 is a 1C cycle performance curve of the batteries assembled with the cathode materials of examples 12 to 15 and comparative example 7.
Fig. 10 is a graph showing the rate performance of the batteries assembled from the positive electrode materials of examples 12 to 15 and comparative example 7.
Fig. 11 is an SEM image of the electrode sheet of example 13 after 100 weeks of cycling.
Fig. 12 is an SEM image of the comparative example 7 electrode sheet after 100 weeks of cycling.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Example 1:
18.9912g Ni are weighed respectively 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 10.2099g LiOH H 2 O and 6.2829gLi 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=2:1 (i.e. n (Li) in flux: n (ni+co+mn) =2:1 in precursor). Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. And repeatedly washing for 3 times, carrying out suction filtration without the pH value decreasing, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 600 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 2:
18.9912g Ni are weighed respectively 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 10.2099g LiOH H 2 O and 6.2829gLi 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=2:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 timesSuction filtration is carried out, and the filter cake is put into a vacuum drying oven for drying for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 650 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 3:
18.9912g Ni are weighed respectively 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 10.2099g LiOH H 2 O and 6.2829gLi 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=2:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 700 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 4:
18.9912g Ni are weighed respectively 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 10.2099g LiOH H 2 O and 6.2829gLi 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=2:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and cooling along with the furnaceTo room temperature. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 750 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 5:
18.9912g Ni are weighed respectively 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 10.2099g LiOH H 2 O and 6.2829gLi 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=2:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 800 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 6:
18.9912g Ni are weighed respectively 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 10.2099g LiOH H 2 O and 6.2829gLi 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=2:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 850 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 7:
18.9912g Ni are weighed respectively 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 10.2099g LiOH H 2 O and 6.2829gLi 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=2:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 8 hours at 750 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 8:
18.9912g Ni are weighed respectively 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 10.2099g LiOH H 2 O and 6.2829gLi 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=2:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 1h, standing the mixture until the solution is completely layered, pouring out the upper layer of solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 750 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 9:
18.9912gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 5.8707g LiOH H 2 O and 3.6127g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=1.15:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing into a beaker, adding 100mL of deionized water, stirring uniformly, measuring the pH value, and continuing stirring for 30min, wherein the feed-liquid ratio is 1:25And standing until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 750 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 10:
18.9912gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 6.3812g LiOH H 2 O and 3.9268g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=1.25:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 750 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 11:
18.9912gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 7.6574g LiOH H 2 O and 4.7122g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=1.5:1. Grinding and mixing in a mortar, placing in a crucible after the powder is uniformly mixed, and moving into an atmosphere furnace with oxygen for segment calcinationHeating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, heating to 850 ℃ for 15 hours, and cooling to room temperature along with a furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 750 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 12:
9.4956gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 5.0355g LiOH H 2 O and 1.6799g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =84:16, li/me=1.6:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 750 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 13:
9.4956gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 5.3502g LiOH H 2 O and 1.7849g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =84:16, li/me=1.7:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 750 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 14:
9.4956gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 5.6649g LiOH H 2 O and 1.8899g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =84:16, li/me=1.8:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, vacuum filtering, and placing the filter cake into a vacuum drying oven at 80deg.CDrying for 24h. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 750 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Example 15:
9.4956gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 5.9796g LiOH H 2 O and 1.9949g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =84:16, li/me=1.9:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 750 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 A single crystal positive electrode material.
Comparative example 1:
18.9912gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 5.3602g LiOH H 2 O and 3.2985g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=1.05:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with 300 mesh sieve to obtain three productsThe anode material is prepared into LiNi 0.88 Co 0.09 Mn 0.03 O 2 The positive electrode material is a polycrystalline material.
Comparative example 2:
18.9912gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 5.3602g LiOH H 2 O and 3.2985g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=1.05:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 10min, standing the mixture until the solution is completely layered, and carrying out suction filtration. The filter cake was dried in a vacuum oven at 80℃for 24h. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 The positive electrode material is a polycrystalline material.
Comparative example 3:
18.9912gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 5.3602g LiOH H 2 O and 3.2985g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=1.05:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Straight lineAnd (5) completely layering the solution, and carrying out suction filtration. The filter cake was dried in a vacuum oven at 80℃for 24h. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 The positive electrode material is a polycrystalline material.
Comparative example 4:
18.9912gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 5.3602g LiOH H 2 O and 3.2985g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=1.05:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 10min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 The positive electrode material is a polycrystalline material.
Comparative example 5:
18.9912gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 5.3602g LiOH H 2 O and 3.2985g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=1.05:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing in a beaker, adding 100mL of deionized waterThe ratio of the feed to the liquid is 1:25, the pH value is measured after uniform stirring, the stirring is continued for 30min, the solution is kept stand until the solution is completely layered, the upper layer solution is poured out, 100mL of deionized water is added, and the pH value is measured again after uniform stirring. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 The positive electrode material is a polycrystalline material.
Comparative example 6:
9.4956gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 3.3045g LiOH H 2 O and 1.1024g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =84:16, li/me=1.05:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 830 ℃ for 20 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 750 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 The positive electrode material is a polycrystalline material.
Comparative example 7:
9.4956gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 3.3045g LiOH H 2 O and 1.1024g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =84:16, li/me=1.05:1. Grinding and mixing in a mortar, placing in a crucible after the powder is uniformly mixed, and transferring into an atmosphere furnace with oxygen for segmented calcination at 5 DEG CThe heating rate per min is firstly increased to 500 ℃ for 4 hours, then increased to 780 ℃ for 14 hours, and finally cooled to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 750 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 The positive electrode material is a polycrystalline material.
Comparative example 8:
18.9912gNi are respectively weighed 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor, 5.3602g LiOH H 2 O and 3.2985g Li 2 CO 3 ，n(LiOH·H 2 O):n(Li 2 CO 3 ) =74:26, li/me=1.05:1. Grinding and mixing in a mortar, placing the powder in a crucible after the powder is uniformly mixed, transferring the crucible into an atmosphere furnace filled with oxygen for segmented calcination, heating to 500 ℃ at a heating rate of 5 ℃/min for 4 hours, heating to 750 ℃ for 5 hours, continuously heating to 850 ℃ for 15 hours, and finally cooling to room temperature along with the furnace. Crushing, grinding and sieving with a 300-mesh sieve to obtain the ternary positive electrode material. Weighing 4g of positive electrode material, placing the positive electrode material into a beaker, adding 100mL of deionized water, uniformly stirring the mixture at a feed-liquid ratio of 1:25, measuring the pH value, continuously stirring the mixture for 30min, standing the mixture until the solution is completely layered, pouring out the upper layer solution, adding 100mL of deionized water, uniformly stirring the mixture, and measuring the pH value again. Repeatedly washing for 3 times, performing suction filtration, and putting the filter cake into a vacuum drying oven to be dried for 24 hours at 80 ℃. Placing the mixture in a corundum crucible again, calcining the mixture for 4 hours at 750 ℃ in an oxygen atmosphere, and cooling the mixture to room temperature along with a furnace. Grinding and sieving to obtain LiNi 0.88 Co 0.09 Mn 0.03 O 2 The positive electrode material is a polycrystalline material.
Comparative example 9:
reference example 4 differs in that lithium sulfate was used instead of lithium carbonate.
The positive electrode materials prepared in examples 1 to 15 and comparative examples 1 to 8 were prepared into 2032-type button-type analog batteries, and their electrochemical properties were measured. The method comprises the following specific steps: (1) Respectively weighing active substances, conductive acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 80:10:10, firstly dissolving PVDF into a proper amount of N-methylpyrrolidone (NMP), then adding the uniformly mixed active substances and acetylene black powder into NMP, and uniformly stirring to prepare slurry; (2) Uniformly coating the slurry on an aluminum foil substrate, putting the wet electrode into a vacuum drying oven, and drying at 80 ℃ for 12 hours; (3) In a dry vacuum glove box, the simulated cells were assembled and the electrochemical performance test results are shown in table 1.
TABLE 1 electrochemical Properties of the cathode materials of examples 1 to 15 and comparative examples 1 to 8 (2.8 to 4.5V)
As can be seen from table 1, li/me=2:1, n (lioh·h 2 O):n(Li 2 CO 3 ) Under the condition of =74:26, the single-crystal high-nickel ternary cathode materials of examples 1 to 6 show the same rule in terms of first-time charge-discharge efficiency as the initial firing temperature increases and then the first-time discharge specific capacity tends to be increased. Therefore, the calcination temperature is preferably 700 to 750 ℃. Wherein the capacity retention rate reached 89.1% after 100 weeks of cycling at 1C rate in example 3; the specific capacity for the first discharge was 182.0mAh/g in example 4. The positive electrode material particles have single crystal morphology, the primary particle size is mostly more than 3 mu m, and the dispersibility is good. As shown in fig. 1 and 2. In addition to the initial polycrystalline morphology, i.e., the primary particles agglomerated into secondary particles, comparative example 1, which had no subsequent water washing and calcination after water washing, had a morphology in which a small portion of the spheroidal secondary particles split into primary particles, as shown in fig. 6, with a Li/Me molar ratio of 1.05:1. The cycle stability of example 3 was better than that of comparative example 1, and that of comparative example 8, which had been back-burned with water, but lower than that of comparative example 5, which had not been back-burned with water. As can be seen from a comparison of example 4 and comparative example 8, the Li/Me molar ratio is 2:1, which is higher than 1.05:1 in terms of the first charge and discharge efficiency. Example 10 and comparative example 5 comparisonIt is known that the first charge and discharge efficiency can be higher by adding the calcination step after washing. On the basis of example 4, the burn-back time was prolonged to 8 hours or the water washing time was increased to 1 hour, as shown in fig. 3 and 4, the primary particles were slightly agglomerated, but the first discharge capacity was improved, and the cycle stability of example 7 was improved. Select n (LiOH. H) 2 O):n(Li 2 CO 3 ) Comparative example 8, in which the molten salt system=74:26/84:16, li/me=1.05:1, is polycrystalline in morphology, and the overall electrochemical performance is superior to that of comparative example 1 by water washing and backfire treatment. And the positive electrode material with Li/Me=1.15-1.9:1 is in a single crystal morphology, as shown in figures 5 and 6, and has better particle dispersibility. The first charge-discharge efficiency and cycling stability of the single crystalline materials of examples 12-15 are superior to comparative example 7, which is a distinct polycrystalline morphology with fusion between the agglomerate particles to form larger particle size agglomerate particles, see fig. 8. The initial discharge specific capacity of 0.2C of example 13 is 201.8mAh/g, the initial charge-discharge efficiency is 83.0%, and after 1C is cycled for 100 weeks, the discharge specific capacity can reach 162.3mAh/g, and the capacity retention rate is 86.7%, as shown in FIG. 9. As can be seen from fig. 10, the 159.9mAh/g capacity of example 13 was higher than 153.3mAh/g of comparative example 7 at 10C discharge, and the 150.1mAh/g capacity of example 12 was also closer to comparative example 7. When the 0.2C discharge was restored, the capacities of the materials of examples 12 to 14 were restored to 96.8%, 96.2%, 92.6% and 88.6% of their initial capacities, respectively, each higher than 86.8% of comparative example 7. The single-crystal type high nickel material has good multiplying power performance. Fig. 11 and 12 are SEM images of the electrode sheets of example 13 and comparative example 7, respectively, after 100 weeks of cycling. It can be seen that the particles with single crystal morphology remain intact through multiple charge and discharge cycles, the arrangement is relatively compact, and no obvious cracks exist in the particles with polycrystalline morphology. Therefore, the electrode structure using the single-crystal type high-nickel positive electrode material as an active material is stable, thereby exhibiting good cycle performance and reversibility of high-rate discharge cycle.
Selection of LiOH-Li 2 CO 3 The mixed molten salt is used as a fluxing agent, the lithium ratio (Li/Me) is important, and when the Li/Me exceeds 1.15, the single crystal material can be obtained. But can obtain good cycle stability and doubling under proper process conditionsSingle crystal material of rate performance; when Li/Me is 1.05, the polycrystalline material is obtained through one sintering. In addition, the secondary sintering condition and the water washing condition have a certain influence on the electrochemical performance of the single crystal material.
Claims (3)
1. The preparation method of the single-crystal high-nickel ternary positive electrode material for the high-voltage lithium ion battery is characterized by comprising the following steps of:
1) Ni is added with 0.88 Co 0.09 Mn 0.03 (OH) 2 Precursor and LiOH H 2 O、Li 2 CO 3 Grinding in a mortar, and mixing uniformly; wherein LiOH.H 2 O and Li 2 CO 3 Constructing a binary fluxing agent, wherein the total mole percentage of the fluxing agent is 100%, and LiOH.H in the fluxing agent 2 The mole fraction of O is: 74% -84%, the rest is Li 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the Li and Ni in flux 0.88 Co 0.09 Mn 0.03 (OH) 2 The mol ratio of the sum of all metal atoms of the precursor is (1.15-2) 1;
2) Placing the uniformly mixed material obtained in the step 1) in an oxygen atmosphere for sectional calcination, firstly heating to 400-600 ℃ at a heating rate of 3-5 ℃/min for 2-6 h, then heating to 750 ℃ for 5-15 h, continuously heating to 800-900 ℃ for 5-15 h, finally cooling to room temperature along with a furnace, crushing and grinding, and sieving with a 300-mesh sieve to obtain a ternary anode material;
3) Mixing the material obtained in the step 2) with deionized water, stirring for 20-40 min until the solution is completely layered, pouring the upper layer solution, adding deionized water, repeatedly washing for 3 times until the pH value is no longer reduced, carrying out suction filtration, putting the filter cake into a vacuum drying box, drying for 20-28 h at 70-90 ℃, putting the filter cake into a corundum crucible again, calcining for 4-8 h at 600-850 ℃ preferably 700-750 ℃ in an oxygen atmosphere, cooling to room temperature along with a furnace, grinding and screening, and obtaining the single crystal type high nickel ternary positive electrode material for the high voltage lithium ion battery.
2. The method according to claim 1, wherein Li in the flux is mixed withNi 0.88 Co 0.09 Mn 0.03 (OH) 2 The molar ratio of the sum of all metal atoms of the precursor is (1.6-1.9): 1.
3. The process according to claim 1, wherein the calcination temperature in step 3) is 700 to 750 ℃ in an oxygen atmosphere.
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