CN114956210A - Single crystal lithium ion battery anode material with different layered structures and preparation method and application thereof - Google Patents
Single crystal lithium ion battery anode material with different layered structures and preparation method and application thereof Download PDFInfo
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- CN114956210A CN114956210A CN202210744436.6A CN202210744436A CN114956210A CN 114956210 A CN114956210 A CN 114956210A CN 202210744436 A CN202210744436 A CN 202210744436A CN 114956210 A CN114956210 A CN 114956210A
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- 239000013078 crystal Substances 0.000 title claims abstract description 74
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 58
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000010405 anode material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 238000005342 ion exchange Methods 0.000 claims abstract description 13
- 238000000975 co-precipitation Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 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 claims abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 10
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 47
- 239000011572 manganese Substances 0.000 claims description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 229910013553 LiNO Inorganic materials 0.000 claims description 3
- 241000080590 Niso Species 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 12
- 239000012071 phase Substances 0.000 abstract description 10
- -1 lithium hexafluorophosphate Chemical compound 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 abstract 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 230000001276 controlling effect Effects 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 229910052723 transition metal Inorganic materials 0.000 description 11
- 150000003624 transition metals Chemical class 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 239000012716 precipitator Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- SFBJBHRQDZBZAF-UHFFFAOYSA-M [Mn]O Chemical compound [Mn]O SFBJBHRQDZBZAF-UHFFFAOYSA-M 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910003548 Li(Ni,Co,Mn)O2 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- 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
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/48—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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Abstract
The invention discloses a single crystal lithium ion battery anode material with different layered structures and a preparation method and application thereof, belonging to the technical field of lithium ion battery anode materials. Using liquid-phase Li + /Na + Ion exchange method, firstly adopting coprecipitation and high-temperature calcination method to synthesize single crystal sodium-containing layered oxide (Na) m [Li x Ni y Co z Mn 1‑x‑y‑z ]O 2 ) Adding the mixture into organic solution containing lithium salt (lithium hexafluorophosphate or lithium perchlorate), filtering and washing to obtain different types of layered oxides (Li) m [Li x Ni y Co z Mn 1‑x‑y‑z ]O 2 ) A compound is provided. The method can be used for preparing the O3 phase layered oxide with stable thermodynamics and preparing the metastable O2 phase layered structure, the prepared oxide particles are all composed of micron-sized single crystal particles, the grain size is distributed between 1 and 6 microns, the grain size is controllable, the consistency is good, the cycling stability is excellent, the application range is wide (4.3 to 4.6V), and the method can be widely applied to the markets of electronic products and power automobiles.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, relates to a single crystal lithium ion battery anode material with different layered structures, and a preparation method and application thereof, and particularly relates to a lithium ion battery anode material prepared by liquid phase Li + /Na + A method for preparing single crystal anode materials with different layered structures by an ion exchange method.
Background
Energy storage batteries are of great importance in solving energy and environmental problems facing the human society. Among various types of batteries, lithium ion batteries have been widely used in electric tools and electronic devices such as electric vehicles, portable electronic devices, and robots, by virtue of their high energy density and no memory effect. Among the various lithium ion battery elements, the positive electrode is most costly and expensive, and has a significant impact on the cost and overall performance of the lithium ion battery. Therefore, the development of the positive electrode is critical to the success of lithium ion batteries. The anode material of the lithium ion battery mainly comprises lithium cobaltate (LiCoO) 2 ) Lithium nickelate (LiNiO) 2 ) Lithium iron phosphate (LiFePO) 4 ) And the like. Although lithium cobaltate shows better electrochemical performance, the lithium cobaltate has higher cost and certain toxicity; the cycle performance and the thermal stability of the lithium nickelate are poor; the voltage of the lithium iron phosphate is only about 3.3V, which is lower than that of other anode materials, and the application of commercial production is difficult. Li (Ni, Co, Mn) O 2 Can be balanced and regulated in the aspects of specific energy, cyclicity, safety and cost, and is widely concerned. However, since Li ion extraction/insertion during charge and discharge may cause structural change of the material and irreversible Li loss, phase transition may easily occur, resulting in voltage decay and poor rate performance,preventing its further use. Therefore, in order to improve the capacity and the cycle stability of the lithium ion battery, the adjustment of the stacking arrangement of oxygen is a key point of research.
The preparation of the layered positive electrode material generally comprises two steps: preparing a precursor by a wet chemical method and preparing a final lithium intercalation oxide by a high-temperature solid phase method. However, high-temperature calcination generally generates a thermodynamically stable O3 phase layer material, and the regulation space of the oxygen accumulation mode in the layered structure is limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide single crystal lithium ion battery anode materials with different layered structures, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of single crystal lithium ion battery anode materials with different layered structures, which comprises the following steps: firstly, adopting coprecipitation and high-temperature calcination method to synthesize monocrystal sodium-containing layered oxide Na m [Li x Ni y Co z Mn 1-x-y-z ]O 2 Then adding the lithium salt into organic solution containing lithium salt for ion exchange treatment, and then filtering and washing to prepare the anode material Li of the single crystal lithium ion battery with different layered structures m [Li x Ni y Co z Mn 1-x-y-z ]O 2 (ii) a Wherein m is more than or equal to 0.50 and less than or equal to 1.00, and x is more than or equal to 0.00 and less than or equal to 0.33; y is more than or equal to 0.00 and less than or equal to 0.50; z is more than or equal to 0.00 and less than or equal to 0.50.
Preferably, the method for preparing the single crystal lithium ion battery cathode material with different layered structures comprises the following steps:
step 1, coprecipitation:
according to the chemical formula Na m [Li x Ni y Co z Mn 1-x-y-z ]O 2 Weighing nickel salt, cobalt salt and manganese salt raw materials according to the proportion (x is more than or equal to 0.00 and less than or equal to 0.33; y is more than or equal to 0.00 and less than or equal to 0.50; z is more than or equal to 0.00 and less than or equal to 0.50), and adding deionized water into the raw materialsStirring to prepare 0.5-3 mol/L -1 A salt solution; diluting the strong ammonia water into 1-10 mol/L ammonia water solution by using deionized water; and preparing 2-8 mol/L precipitator solution from sodium hydroxide by using deionized water. Then 2L of deionized water is added into a 10L reaction kettle, inert gas nitrogen is introduced to remove oxygen, and the inlet flow of the nitrogen is 2L/min; respectively adding a salt solution, an alkali solution and an ammonia water solution into a reaction kettle by a peristaltic pump, controlling the feeding speed of the salt solution to be 0.5-10 ml/min and the feeding speed of the ammonia solution to be 0.2-5 ml/min, controlling the feeding flow rate of a sodium hydroxide solution to control the pH value of the solution in the reaction kettle to be 10.0-12.5, controlling the temperature to be 40-70 ℃, and controlling the stirring speed to be 300-600 r/min; after reacting for 1-80 h, filtering, washing and drying a product obtained in the reaction kettle to obtain a hydroxide precursor material;
step 2, calcining:
the hydroxide precursor material obtained in the step 1 is prepared according to the chemical formula Na m [Li x Ni y Co z Mn 1-x-y-z ]O 2 The sodium salt and the lithium salt are weighed according to the proportion (m is more than or equal to 0.50 and less than or equal to 1.00), are uniformly mixed and then are put into a muffle furnace, the heating rate is 3-10 ℃/min, the temperature is raised to 400-600 ℃ in the air atmosphere, the pre-sintering is carried out for 2-8 h, then the calcination is carried out for 6-20 h at 700-900 ℃, and the natural cooling is carried out to the room temperature, so as to obtain the P2, P3 or O3 type monocrystal sodium ion battery layered oxide Na m [Li x Ni y Co z Mn 1-x-y-z ]O 2 ；
Step 3, ion exchange:
immersing the monocrystal layered oxide obtained in the step 2 into an organic solution of lithium salt, wherein the concentration is 0.1-2 mol/L, the immersion time is 0.1-3 hours, then carrying out centrifugal separation, washing with ethanol for 2-3 times, drying and collecting the obtained product, namely O2 or O3 type monocrystal lithium ion layered oxide Li m [Li x Ni y Co z Mn 1-x-y-z ]O 2 ；
The more preferable technical scheme of the invention is as follows:
further, in step 1, the nickel salt is NiSO 4 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Ni(CH 3 COO) 2 ·4H 2 O or NiCl 2 ·6H 2 O; the manganese salt is MnSO 4 ·H 2 O、Mn(NO 3 ) 2 ·4H 2 O、Mn(CH 3 COO) 2 ·4H 2 O or MnCl 2 ·4H 2 O; the cobalt salt is CoSO 4 ·7H 2 O,CoCl 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O or Co (CH) 3 COO) 2 ·4H 2 O。
Further, in step 2, the sodium salt is Na 2 CO 3 、NaOH、NaNO 3 Or NaCH 3 COO; the lithium salt is Li 2 CO 3 、LiNO 3 、LiOH·H 2 O or LiCH 3 COO。
Further, in step 3, the lithium salt is LiPF 6 Or LiClO 4 Any one of the above.
Further, in step 3, Na is added m [Li x Ni y Co z Mn 1-x-y-z ]O 2 The ratio of the lithium salt to the organic solution is 1: 20-1: 200 mg/mu L.
Further, in step 3, the organic solvent is any one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC) and dimethyl carbonate (DMC).
The invention also discloses the single crystal lithium ion battery anode material with different layered structures prepared by the preparation method, the single crystal lithium ion battery anode material with different layered structures has an O3 phase layered or metastable O2 phase layered structure and consists of micron-sized single crystal particles, the grain size is distributed between 1 and 6 microns, and the grain size is controllable.
The invention also discloses application of the single crystal lithium ion battery anode materials with different layered structures in preparation of lithium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of single crystal lithium ion battery anode materials with different layered structures, which adopts a liquid phase ion exchange method and firstly adopts coprecipitation to prepare hydroxideCalcining the precursor mixed with sodium and lithium to obtain single crystal particles with different layered structures, immersing the particles in lithium salt organic solution, filtering and washing to obtain O2 or O3 type single crystal layered oxide (Li 2 or O3 type single crystal layered oxide) m [Li x Ni y Co z Mn 1-x-y-z ]O 2 ) The preparation method can prepare not only O3 phase layered oxide with stable thermodynamics, but also O2 phase layered structure with metastable state, which is difficult to realize by common high temperature solid idea, and the layered anode material prepared by the method has unique structural characteristics and excellent electrochemical performance, uniform distribution of single crystal particles, controllable particle size, good batch uniformity, simple process, easy operation and stable and reliable material structure, and compared with the traditional high temperature solid phase reaction, the layered anode material not only can obtain various O2, O3 and T2 layered structures, but also has unique structural characteristics and excellent electrochemical performance. In addition, Li + /Na + The ion exchange reaction is carried out at room temperature with single crystal Na m [Li x Ni y Co z Mn 1-x-y-z ]O 2 The template can effectively prepare single crystal lithium ion ternary anode materials with different layered structures, and is convenient for industrial popularization.
The single crystal lithium ion battery anode material with different layered structures prepared by the method has excellent cycle performance, the capacity retention rate of the material is up to more than 93% after 25 cycles under the conditions of 2.0-4.8V and 0.1C, and the material can be widely applied to the markets of electronic products and power automobiles.
Drawings
Fig. 1 is a first charge-discharge curve of a single crystal O2-type layered cathode material prepared in example 1 of the present invention at a 0.1C rate;
FIG. 2 is an X-ray diffraction pattern of a layered cathode material of single crystal O3 type prepared in example 2 of the present invention;
FIG. 3 is a SEM image of a layered cathode material of single crystal O3 type prepared in example 3 of the present invention;
FIG. 4 shows the cycle performance of the single crystal O2/O3 composite layered positive electrode material prepared in example 4 of the present invention;
fig. 5 is an X-ray diffraction pattern of a single crystal O2-type layered cathode material prepared in example 5 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
example 1:
in this example, the formula is shown as Na 2/3 [Li 0.2 Ni 0.2 Co 0.1 Mn 0.5 ]O 2 And (4) batching.
A method for preparing single crystal lithium ion battery anode materials with different layered structures comprises the following steps:
step 1, coprecipitation:
according to the molar ratio of nickel, cobalt and manganese elements of 0.20.2:0.5 respectively weighing corresponding NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 Adding three salts O, and adding deionized water to prepare a transition metal salt solution with the concentration of 3 mol/L; weighing sodium hydroxide solid, adding the sodium hydroxide solid into deionized water to prepare a precipitator solution with the concentration of 8mol/L, adding 25% ammonia water into the deionized water, and diluting the ammonia water into an ammonia water solution with the concentration of 10 mol/L; then 2L of deionized water is added into a 10L reaction kettle, and nitrogen is introduced, wherein the inlet flow of the nitrogen is 2L/min; respectively injecting a transition metal salt solution and an ammonia solution into the reaction kettle from a feed inlet at feed speeds of 0.5ml/min and 0.2ml/min by using a peristaltic pump, regulating and controlling the feed flow rate of a sodium hydroxide solution to control the pH value of a reaction system to be 11.1, controlling the reaction temperature to be 70 ℃, and controlling the stirring speed of a stirring paddle to be 600 r/min; after reacting for 80h, filtering, washing and drying to obtain a precursor material;
step 2, calcining:
mixing the hydroxide precursor particles obtained in the step 1 with Na 2 CO 3 、Li 2 CO 3 Mixing, wherein the total molar amount of the transition metal salt and the ratio of sodium to lithium are 0.8:0.67:0.2, putting the obtained mixture into a ball mill, uniformly mixing, putting the mixture into a muffle furnace, heating to 600 ℃ at the heating rate of 10 ℃/min, presintering for 8 hours, heating to 900 ℃ at the heating rate of 10 ℃/min, and preserving heat for 20 hours to obtain a single-crystal P2 type sodium ion layered oxide;
step 3, ion exchange:
immersing the single crystal P2 type layered oxide obtained in the step 2 into 2mol/L LiPF 6 In the organic solution, the solvent is EC, DEC and DMC (volume ratio is 1:1:1), the sodium ion layered oxide and LiPF 6 The proportion of the organic solution is 1:20 mg/mul, after soaking for 0.1h, centrifugal separation is carried out, ethanol is used for washing for 3 times, and the product obtained after drying and collection is O2 type single crystal lithium ion layered oxide Li 2/3 [Li 0.2 Ni 0.2 Co 0.1 Mn 0.5 ]O 2 。
The O2 type single crystal lithium ion layered oxide prepared in this example has a hexahedral morphology, a length of about 2 μm and a thickness of about 0.5. mu.m.
The process for testing the charge and discharge performance of the cathode material prepared in the embodiment is as follows:
weighing a certain amount of the positive electrode material prepared in the embodiment, acetylene black and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, adding the positive electrode material, the acetylene black and the binder polyvinylidene fluoride (PVDF) into N-methylpyrrolidone (NMP) to prepare slurry, uniformly coating the slurry on an aluminum foil, drying the aluminum foil in vacuum for 12 hours at 100 ℃, and cutting the aluminum foil into pole pieces with the diameter of 12mm by using a mold; a lithium metal sheet as a cathode, a Celgard 2400 commercial polypropylene membrane as a separator, and an electrolyte LP30 were assembled into a button cell model CR2032 in a glove box filled with inert gas.
The electrochemical performance test of the battery is carried out under the conditions that the voltage range is 2.0-4.8V and the temperature is 0.1C, and the result shows that the positive electrode material Li prepared in the embodiment 2/3 [Li 0.2 Ni 0.2 Co 0.1 Mn 0.5 ]O 2 The first charge and discharge capacity at 0.1C rate was 208 and 216mAh/g, respectively, as shown in fig. 1.
Example 2
In this example, the formula is shown as Na [ Li ] 1/3 Mn 2/3 ]O 2 And (4) batching.
A method for preparing single crystal lithium ion battery anode materials with different layered structures comprises the following steps:
step 1, coprecipitation:
weighing MnSO 4 ·H 2 Adding deionized water into the O solid powder to prepare a solution with the concentration of 2 mol/L; weighing sodium hydroxide solid, adding the sodium hydroxide solid into deionized water to prepare a precipitator solution with the concentration of 4mol/L, adding 25% ammonia water into the deionized water, and diluting the ammonia water into an ammonia water solution with the concentration of 1 mol/L; then 2L of deionized water is added into a 10L reaction kettle, and nitrogen is introduced, wherein the inlet flow of the nitrogen is 2L/min; injecting a transition metal salt solution and an ammonia solution into the reaction kettle from a feed inlet by using a peristaltic pump at feed speeds of 10ml/min and 5ml/min respectively, regulating and controlling the feed flow rate of a sodium hydroxide solution to control the pH value of a reaction system to be 12.5, controlling the reaction temperature to be 60 ℃, and controlling the stirring speed of a stirring paddle to be 600 r/min; after reacting for 30h, filtering, washing and drying to obtain the productA bulk material;
step 2, calcining:
the hydroxide precursor particles obtained in the step 1 and NaCH 3 COO、LiCH 3 COO, mixing the molar weight of manganese and the ratio of sodium to lithium of 0.67:1.0:0.33, putting the obtained mixture into a ball mill, uniformly mixing, putting the mixture into a muffle furnace, heating to 400 ℃ at the heating rate of 3 ℃/min, presintering for 4 hours, heating to 900 ℃ at the heating rate of 3 ℃/min, and preserving heat for 12 hours to obtain a single-crystal O3 type sodium ion layered oxide;
step 3, ion exchange:
immersing the layered oxide of single crystal O3 type obtained in step 2 in 0.1mol/L LiClO 4 In the organic solution, the solvent is PC, oxide powder and LiClO 4 The proportion of the organic solution is 1:200 mg/mul, after soaking for 3h, centrifugal separation is carried out, ethanol is used for washing for 2 times, and the product obtained after drying and collection is O3 type monocrystal lithium ion layered oxide Li [ Li 1/3 Mn 2/3 ]O 2 。
Single crystal oxide Li [ Li ] prepared in this example 1/3 Mn 2/3 ]O 2 See fig. 2, from which it can be seen that all diffraction peaks are assigned to O3 type layered structure, and the space group is C2/m, wherein the diffraction peak around 22 ° is a honeycomb superlattice structure.
And (3) testing the charge and discharge performance: the test method is the same as that of example 1, and the result shows that the first discharge capacity of the O3 type single crystal lithium ion layered positive electrode material prepared in the example at 0.1C is 205 mAh/g.
Example 3
In this example, the compound represented by the formula Na 0.5 [Mn]O 2 And (4) batching.
A method for preparing single crystal lithium ion battery anode materials with different layered structures comprises the following steps:
step 1, coprecipitation:
weighing MnCl 2 ·4H 2 Adding deionized water into the O solid powder to prepare a solution with the concentration of 0.5 mol/L; weighing sodium hydroxide, adding into deionized water to obtain 2mol/L precipitant solution, adding strong ammonia waterAdding deionized water, and diluting to obtain an ammonia water solution with the concentration of 5 mol/L; then 2L of deionized water is added into a 10L reaction kettle, and nitrogen is introduced, wherein the inlet flow of the nitrogen is 2L/min; injecting a transition metal salt solution and an ammonia solution into the reaction kettle from a feed inlet by using a peristaltic pump at the feeding speeds of 2ml/min and 0.8ml/min respectively, regulating and controlling the feeding flow rate of a sodium hydroxide solution to control the pH value of a reaction system to be 11.5, controlling the reaction temperature to be 52 ℃, and controlling the stirring speed of a stirring paddle to be 300 r/min; after reacting for 1h, filtering, washing and drying to obtain a precursor material;
step 2, calcining:
mixing the black precursor particles obtained in the step 1 with Na 2 CO 3 Mixing, wherein the molar weight of manganese and the ratio of sodium are 0.5:1.0, placing the obtained mixture in a ball mill, uniformly mixing, then placing the mixture in a muffle furnace, heating to 550 ℃ at the heating rate of 5 ℃/min, presintering for 6 hours, then heating to 700 ℃ at the heating rate of 5 ℃/min, and preserving heat for 6 hours to obtain the single crystal P3 type sodium ion layered oxide;
step 3, ion exchange:
immersing the single crystal P3 type layered oxide obtained in step 2 into 1.5mol/L LiPF 6 In organic solution, the solvent is EC and DMC (volume ratio is 1:1), oxide powder and LiPF 6 The proportion of the organic solution is 1:100 mg/mul, after soaking for 2h, centrifugal separation is carried out, ethanol is used for washing for 3 times, and the product obtained after drying and collection is O3 type single crystal lithium ion layered oxide Na 0.5 [Mn]O 2 。
The morphology of the lithium ion layered oxide prepared in this example is shown in fig. 3, and it can be seen from the figure that the single crystal particles are mainly hexagonal, uniformly distributed, and have a particle size of about 1 μm.
And (3) testing the charge and discharge performance: the test method is the same as that of the embodiment 1, and the result shows that the first discharge capacity of the core-shell structure cathode material prepared by the embodiment at 0.1 ℃ reaches 193 mAh/g.
Example 4
In this example, the formula is shown as Na 0.8 [Li 0.05 Ni 0.1 Co 0.5 Mn 0.35 ]O 2 And (4) batching.
A method for preparing single crystal lithium ion battery anode materials with different layered structures comprises the following steps:
step 1, coprecipitation:
weighing corresponding Ni (NO) according to the molar ratio of nickel, cobalt and manganese elements of 0.1:0.5:0.35 3 ) 2 ·6H 2 O、Mn(NO 3 ) 2 ·4H 2 O and Co (NO) 3 ) 2 ·6H 2 Adding three salts O, and adding deionized water to prepare a transition metal salt solution with the concentration of 2 mol/L; weighing sodium hydroxide, adding the sodium hydroxide into deionized water to prepare a precipitator solution with the concentration of 4mol/L, and adding strong ammonia water into the deionized water to dilute the strong ammonia water into an ammonia water solution with the concentration of 3 mol/L; then 2L of deionized water is added into a 10L reaction kettle, and nitrogen is introduced, wherein the inlet flow of the nitrogen is 2L/min; injecting a transition metal salt solution and an ammonia solution into the reaction kettle from a feed inlet by using a peristaltic pump at feed speeds of 1ml/min and 1.5ml/min respectively, regulating and controlling the feed flow rate of a sodium hydroxide solution to control the pH value of a reaction system to be 10, controlling the reaction temperature to be 40 ℃, and controlling the stirring speed of a stirring paddle to be 500 r/min; after reacting for 20 hours, filtering, washing and drying to obtain a precursor material;
step 2, calcining:
mixing the precursor particles obtained in the step 1 with NaOH, LiOH & H 2 O, mixing, wherein the total molar amount of transition metal salt and the ratio of sodium to lithium are 0.95:0.8:0.05, putting the obtained mixture into a ball mill, uniformly mixing, putting the mixture into a muffle furnace, heating to 500 ℃ at the heating rate of 6 ℃/min, presintering for 8 hours, heating to 800 ℃ at the heating rate of 8 ℃/min, and preserving heat for 6 hours to obtain the single crystal P3 and P2 mixed type sodium ion layered oxide;
step 3, ion exchange:
immersing the single crystal P3/P2 mixed type layered oxide obtained in the step 2 into 1.2mol/L LiPF 6 In organic solution, the solvent is EC and DMC (volume ratio is 1:1), oxide powder and LiPF 6 The proportion of the organic solution is 1:150 mg/mu l, after soaking for 1h, centrifugal separation is carried out, ethanol is used for washing for 3 times, and the obtained product is obtained after drying and collection, namely O3 and O2 mixed type monocrystal lithium ion layered oxide Li 0.8 [Li 0.05 Ni 0.1 Co 0.5 Mn 0.35 ]O 2 。
The O3/O2 mixed type single crystal lithium ion layered oxide particle prepared in this example was about 6 μm and had a uniform particle size distribution.
And (3) testing the charge and discharge performance: the test method is the same as that of the example 1, and the result shows that the first discharge capacity of the O3/O2 mixed type single crystal lithium ion layered positive electrode material prepared in the embodiment reaches 198mAh/g under 2.0-4.8V and 0.1C, and the capacity still reaches 186mAh/g after 25 cycles, which is shown in FIG. 4.
Example 5
In this example, the formula is shown as Na 0.6 [Li 0.1 Ni 0.5 Co 0.1 Mn 0.3 ]O 2 And (4) batching.
A method for preparing single crystal lithium ion battery anode materials with different layered structures comprises the following steps:
step 1, coprecipitation:
weighing corresponding Ni (CH) according to the molar ratio of nickel, cobalt and manganese elements of 0.5:0.1:0.3 3 COO) 2 ·4H 2 O、Mn(CH 3 COO) 2 ·4H 2 O and Co (CH) 3 COO) 2 ·4H 2 Adding three salts O, and adding deionized water to prepare a transition metal salt solution with the concentration of 2 mol/L; weighing sodium hydroxide, adding the sodium hydroxide into deionized water to prepare a precipitator solution with the concentration of 4mol/L, adding 25% ammonia water into the deionized water, and diluting the ammonia water into an ammonia water solution with the concentration of 6 mol/L; then 2L of deionized water is added into a 10L reaction kettle, and nitrogen is introduced, wherein the inlet flow of the nitrogen is 2L/min; injecting a transition metal salt solution and an ammonia solution into the reaction kettle from a feed inlet by using a peristaltic pump at the feeding speeds of 2ml/min and 1.2ml/min respectively, regulating and controlling the feeding flow rate of a sodium hydroxide solution to control the pH value of a reaction system to be 11.2, controlling the reaction temperature to be 60 ℃, and controlling the stirring speed of a stirring paddle to be 550 r/min; after reacting for 60 hours, filtering, washing and drying to obtain a precursor material;
step 2, calcining:
mixing the precursor particles obtained in the step 1 with NaNO 3 、LiNO 3 Mixed with transition metals thereofThe total molar amount of salt and the ratio of sodium to lithium are 0.9:0.6:0.1, the obtained mixture is placed in a ball mill to be uniformly mixed, then the mixture is placed in a muffle furnace, the temperature is raised to 500 ℃ at the heating rate of 8 ℃/min, the mixture is presintered for 8 hours, then the temperature is raised to 900 ℃ at the heating rate of 8 ℃/min, and the temperature is maintained for 16 hours, so that the single crystal P2 mixed type sodium ion layered oxide is obtained;
step 3, ion exchange:
immersing the single crystal P3 mixed type lamellar oxide obtained in the step 2 into 0.8mol/L LiPF 6 In organic solution, the solvent is EC, DEC and DMC (volume ratio is 1:1:1), oxide powder and LiPF 6 The proportion of the organic solution is 1:80 mg/mul, after soaking for 0.5h, centrifugal separation is carried out, ethanol is used for washing for 2 times, and the product obtained after drying and collection is O2 type single crystal lithium ion layered oxide Li 0.6 [Li 0.1 Ni 0.5 Co 0.1 Mn 0.3 ]O 2 ；
The O2 type single crystal lithium ion layered oxide element prepared in this example was uniformly distributed in the crystal grains, and the single crystal particle size was about 6 μm. Li prepared in this example 0.6 [Li 0.1 Ni 0.5 Co 0.1 Mn 0.3 ]O 2 See fig. 5, from which it can be seen that all diffraction peaks are attributed to the O2-type layered structure with space group P6 3 mc。
And (3) testing the charge and discharge performance: the test method is the same as that of the embodiment 1, and the result shows that the first discharge capacity of the core-shell structure cathode material prepared by the embodiment at 0.1 ℃ reaches 210 mAh/g.
In conclusion, the method disclosed by the invention can be used for preparing the O3 phase layered oxide with stable thermodynamics and preparing the metastable O2 phase layered structure, the prepared oxide particles are all composed of micron-sized single crystal particles, the grain size is distributed between 1 and 6 microns, the grain size is controllable, the consistency is good, the cycling stability is excellent, the application range is wide (4.3-4.6V), and the method can be widely applied to the markets of electronic products and power automobiles.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of single crystal lithium ion battery anode materials with different layered structures is characterized by comprising the following steps: firstly, adopting coprecipitation and high-temperature calcination method to synthesize monocrystal sodium-containing layered oxide Na m [Li x Ni y Co z Mn 1-x-y-z ]O 2 Then adding the lithium salt into organic solution containing lithium salt for ion exchange treatment, and then filtering and washing to prepare the anode material Li of the single crystal lithium ion battery with different layered structures m [Li x Ni y Co z Mn 1-x-y-z ]O 2 ；
Wherein m is more than or equal to 0.50 and less than or equal to 1.00, and x is more than or equal to 0.00 and less than or equal to 0.33; y is more than or equal to 0.00 and less than or equal to 0.50; z is more than or equal to 0.00 and less than or equal to 0.50.
2. The preparation method of the single crystal lithium ion battery anode material with different laminated structures according to claim 1, is characterized by comprising the following steps:
1) coprecipitation treatment
According to the chemical formula Na m [Li x Ni y Co z Mn 1-x-y-z ]O 2 M is more than or equal to 0.50 and less than or equal to 1.00, x is more than or equal to 0.00 and less than or equal to 0.33, and y is more than or equal to 0.00 and less than or equal to 0.50; z is more than or equal to 0.00 and less than or equal to 0.50, nickel salt, cobalt salt and manganese salt are weighed, and water is added to prepare the nickel salt, cobalt salt and manganese salt into 0.5-3 mol.L -1 Mixing the salt solution, an alkali solution and an ammonia water solution, adjusting the pH value to 10.0-12.5, reacting at 40-70 ℃ for 1-80 h, filtering, washing and drying the product to obtain a hydroxide precursor material;
2) high temperature calcination
The hydroxide precursor material is prepared according to the chemical formula Na m [Li x Ni y Co z Mn 1-x-y-z ]O 2 M is more than or equal to 0.50 and less than or equal to 1.00, x is more than or equal to 0.00 and less than or equal to 0.33, and y is more than or equal to 0.00 and less than or equal to 0.50; weighing sodium salt and lithium salt according to the proportion of z being more than or equal to 0.00 and less than or equal to 0.50, uniformly mixing, calcining for 6-20 h at 700-900 ℃, and naturally cooling to room temperature to obtain P2, P3 or O3 type single crystal sodium ionsLayered oxide Na of subcell m [Li x Ni y Co z Mn 1-x-y-z ]O 2 ；
3) Ion exchange
The layered oxide Na of the single crystal sodium ion battery prepared in the step 2) m [Li x Ni y Co z Mn 1-x-y-z ]O 2 Immersing into an organic solution containing lithium salt, treating for 0.1-3 h, centrifuging, washing and drying to obtain O2 type or O3 type single crystal lithium ion layered oxide Li m [Li x Ni y Co z Mn 1-x-y-z ]O 2 Namely, the single crystal lithium ion battery anode materials with different layered structures.
3. The method for preparing the anode materials of the single crystal lithium ion batteries with different layered structures according to claim 2, wherein in the step 1), the nickel salt is NiSO 4 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Ni(CH 3 COO) 2 ·4H 2 O or NiCl 2 ·6H 2 O; the manganese salt is MnSO 4 ·H 2 O、Mn(NO 3 ) 2 ·4H 2 O、Mn(CH 3 COO) 2 ·4H 2 O or MnCl 2 ·4H 2 O; the cobalt salt is CoSO 4 ·7H 2 O、CoCl 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O or Co (CH) 3 COO) 2 ·4H 2 O。
4. The method for preparing the single crystal lithium ion battery anode material with different laminated structures according to claim 2, wherein in the step 1), the aqueous alkali is 2-8 mol.L prepared by using water to prepare sodium hydroxide -1 A precipitant solution; the concentration of the ammonia water solution is 1-10 mol.L -1 (ii) a And in the reaction process, mechanical stirring treatment is carried out at the speed of 300-600 r/min.
5. The method for preparing the anode material of the single crystal lithium ion batteries with different layered structures according to claim 2,in the step 2), the sodium salt is Na 2 CO 3 、NaOH、NaNO 3 Or NaCH 3 COO; the lithium salt is Li 2 CO 3 、LiNO 3 、LiOH·H 2 O or LiCH 3 COO。
6. The method for preparing the single crystal lithium ion battery anode materials with different layered structures according to claim 2, wherein in the step 2), the sintering system is as follows: from room temperature, heating to 400-600 ℃ at a heating rate of 3-10 ℃/min, pre-sintering for 2-8 h, and then calcining for 6-20 h at 700-900 ℃.
7. The method for preparing the single crystal lithium ion battery cathode material with different laminated structures according to claim 2, wherein in the step 3), the lithium salt is LiPF 6 Or LiClO 4 (ii) a The single crystal sodium ion battery layered oxide Na m [Li x Ni y Co z Mn 1-x-y-z ]O 2 The dosage ratio of the lithium salt to the organic solution containing lithium salt is 1: 20-1: 200 mg/mu L.
8. The method for preparing the single crystal lithium ion battery cathode material with different laminated structures according to claim 2, wherein in the step 3), the organic solution is one or more of ethylene carbonate, propylene carbonate, diethyl carbonate and dimethyl carbonate.
9. The single crystal lithium ion battery anode material with different layered structures prepared by the preparation method of any one of claims 1 to 8 is characterized in that the single crystal lithium ion battery anode material with different layered structures has an O3 phase layered or metastable O2 phase layered structure and consists of micron-sized single crystal particles, the grain size is distributed between 1 and 6 microns, and the grain size is controllable.
10. The use of the single crystal lithium ion battery positive electrode material of different layered structures according to claim 9 in the preparation of lithium ion batteries.
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