CN117059795A - High-entropy alloy modified high-nickel cobalt-free positive electrode material and preparation method thereof - Google Patents
High-entropy alloy modified high-nickel cobalt-free positive electrode material and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 48
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 48
- 239000000956 alloy Substances 0.000 title claims abstract description 43
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000000975 co-precipitation Methods 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- -1 transition metal salt Chemical class 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 3
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 6
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 6
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 5
- HVMFKXBHFRRAAD-UHFFFAOYSA-N lanthanum(3+);trinitrate;hydrate Chemical compound O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVMFKXBHFRRAAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 3
- VXWSFRMTBJZULV-UHFFFAOYSA-H iron(3+) sulfate hydrate Chemical compound O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VXWSFRMTBJZULV-UHFFFAOYSA-H 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000007599 discharging Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000012467 final product Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000001815 facial effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- 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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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention relates to a high-entropy alloy modified high-nickel cobalt-free positive electrode material and a preparation method thereof, belonging to the field of chemical energy storage batteries. Firstly, doping nickel ions, manganese ions and three transition metal ions into a precursor by a coprecipitation method, and then mixing lithium salt and a fourth transition metal salt with the precursor for sintering together to obtain the high-entropy alloy modified high-nickel cobalt-free positive electrode material, wherein the chemical formula of the high-nickel cobalt-free positive electrode material is LiNi x Mn y TM (1‑x‑y)/4 TM (1‑x‑y)/4 TM (1‑x‑y)/4 TM (1‑x‑y)/ 4 O 2 ，0.8<x<1，0<y<0.2，0<x+y<1, tm are each one of transition metal elements. The high-entropy alloy modified high-nickel cobalt-free positive electrode material has more stable structure, increased lithium ion migration rate and excellent high-rate performance and cycle stability. The material obtained by the invention has good multiplying power performance and cycle stability, the process flow is simple, the original industrialized synthetic route is not changed, and industrialization is easy to realize.
Description
Technical Field
The invention relates to a high-entropy alloy modified high-nickel cobalt-free positive electrode material and a preparation method thereof, belonging to the field of chemical energy storage batteries.
Background
The positive electrode material is a key part for limiting the energy density of the lithium ion battery, wherein the high-nickel layered positive electrode has become the most promising positive electrode material of the next generation of lithium ion battery due to the high energy density, high rate performance and better safety. However, high nickel cathode materials currently still have a number of problems including irreversible phase changes, particle microcracking due to stress release during cycling, erosion of the material surface by electrolyte decomposition, and slow kinetics due to cation mixing, especially at high cut-off voltages. Among them, a low-cobalt or cobalt-free high-nickel positive electrode material is attracting more and more attention due to lower cost. However, the low-cobalt or cobalt-free high-nickel cathode material can aggravate cation mixing, thereby seriously affecting the dynamic process and further deteriorating the electrochemical performance. To solve and improve these problems, to meet the performance requirements of people on power batteries, numerous researchers have performed various improvement methods, such as: coating, modifying and designing a precursor process to improve the multiplying power performance, the cycle life and the safety of the anode material.
Disclosure of Invention
The invention aims to provide a high-entropy alloy modified high-nickel cobalt-free positive electrode material and a preparation method thereof, and the high-entropy alloy is modified through two processes of preparing a hydroxide precursor and sintering by coprecipitation, so that doping of the high-entropy alloy on the surface layer and the bulk phase of the positive electrode material is realized, and the high-rate performance and the cycle life of the high-nickel cobalt-free positive electrode are effectively improved by the modification mode.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a high-entropy alloy modified high-nickel cobalt-free positive electrode material has a chemical formula of LiNi x Mn y TM (1-x-y)/4 TM (1-x-y)/4 TM (1-x-y)/4 TM (1-x-y)/4 O 2 ，0.8<x<1，0<y<0.2，0<x+y<1, tm are each one of transition metal elements.
The preparation method of the high-entropy alloy modified high-nickel cobalt-free positive electrode material comprises the steps of firstly doping nickel ions, manganese ions and three transition metal ions into a precursor through a coprecipitation method, and then mixing lithium salt with a fourth transition metal salt to sinter the precursor together to obtain the high-entropy alloy modified high-nickel cobalt-free positive electrode material.
The preparation method of the high-entropy alloy modified high-nickel cobalt-free positive electrode material specifically comprises the following steps:
step (1): taking water as a solution, taking a mixed alkali solution of ammonia water and sodium hydroxide as a complexing agent and a precipitator, dropwise adding a mixed metal salt solution prepared from five metal salts, and obtaining a high-entropy alloy modified high-nickel cobalt-free positive electrode material precursor by a coprecipitation method;
step (2): and mixing the precursor, the lithium salt and the metal salt in a mortar, calcining under oxygen, pre-calcining at a lower temperature, and then calcining at an elevated temperature to obtain the high-entropy alloy modified high-nickel cobalt-free anode material after the sintering process is completed.
In the step (1), five mixed metal salt solutions are mixed aqueous solutions of three of nickel sulfate hexahydrate and manganese sulfate monohydrate, ferric sulfate hydrate, cobalt sulfate heptahydrate, lanthanum nitrate hydrate, titanyl sulfate, zirconium oxychloride, magnesium sulfate, vanadyl sulfate, anhydrous calcium chloride and ammonium molybdate, and the total concentration of metal ions in the mixed metal salt solutions is 1-3 mol/L.
The preparation method of the high-entropy alloy modified high-nickel cobalt-free positive electrode material comprises the following steps of (2) a precursor: lithium salt: the mole ratio of the fourth transition metal salt is 1:1.02-1.08:0.005-0.015, and the fourth transition metal salt is one of hydrated lanthanum nitrate, titanyl sulfate, zirconium oxychloride, magnesium sulfate and anhydrous calcium chloride.
The preparation method of the high-entropy alloy modified high-nickel cobalt-free positive electrode material comprises the following steps of: y: (1-x-y)/4: (1-x-y)/4: (1-x-y)/4: (1-x-y)/4, 0.8< x <1,0< y <0.2,0< x+y <1.
In the preparation method of the high-entropy alloy modified high-nickel cobalt-free positive electrode material, in the step (2), the presintering temperature is 400-500 ℃, and the presintering time is 4-6 hours.
In the step (2), the calcining temperature is 750-830 ℃ and the sintering time is 10-20 hours.
In the step (1), the mixed alkali solution consists of 1-4 mol/L sodium hydroxide solution and 1.5-5 mol/L ammonia water solution, and the pH value is regulated and stabilized to 10-12 by the mixed alkali solution.
The design idea of the invention is as follows: the invention uses low cost, high abundance and applicability as core ideas, and selects a plurality of different metal ion combinations to replace cobalt element in the ternary positive electrode so as to improve the high multiplying power and long cycle performance of the high nickel cobalt-free positive electrode.
The invention has the advantages and beneficial effects as follows:
1. according to the invention, the doping of four metals to the high-nickel cobalt-free positive electrode material is realized by carrying out high-entropy alloy modification in the precursor preparation process and calcining, so that the multiplying power performance and the cycle stability of the material are both obviously improved.
2. The high-entropy alloy modified high-nickel cobalt-free positive electrode material has outstanding high-rate performance, is charged and discharged at a rate of 20 ℃, has a discharge capacity of 135.9mAh/g, and is 3 times that of a nickel-cobalt-manganese ternary positive electrode material with the same molar ratio.
3. The doping method of the invention has simple operation, does not change the existing process flow, obviously improves the electrochemical performance of the cobalt-free anode material, is easy to realize industrial technology, and can be applied to large-scale commercialization.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the final product positive electrode materials prepared in examples 1 to 4. In the figure, the abscissa 2θ represents the diffraction angle (°), and the ordinate density represents the relative Intensity (a.u.).
Fig. 2 is a Scanning Electron Microscope (SEM) of the final product positive electrode materials prepared in examples 1 to 4.
FIG. 3 is a facial scan (EDS) of the energy spectrum of the final product prepared in example 1.
FIG. 4 is a facial scan (EDS) of the energy spectrum of the final product prepared in example 2.
Fig. 5 is a graph showing the charge-discharge electrochemical performance of the assembled batteries of examples 1 to 4 at different rates of 2.7 to 4.4V. In the figure, the abscissa Cycle number represents the number of cycles, and the ordinate Specific capacity represents the specific capacity (mah·g -1 )。
Fig. 6 is a graph showing the electrochemical performance of the assembled batteries of examples 1 to 4 at a 1C rate charge-discharge cycle of 2.7 to 4.4V. In the figure, the abscissa Cycle number represents the number of cycles, and the ordinate Specific capacity represents the specific capacity (mah·g -1 )。
Detailed Description
In a specific implementation process, the invention provides a high-entropy alloy modified high-nickel cobalt-free positive electrode material and a preparation method thereof, and the obtained material is prepared by a coprecipitation method, namely a high-entropy alloy modified nickel-manganese hydroxide precursor and LiOH H 2 O and metal salt are mixed and ground to form mixed solid powder, the mixed solid powder is calcined under oxygen, and the high-entropy alloy modified high-nickel cobalt-free anode material is obtained after cooling, and the specific steps are as follows:
and (2) adding deionized water into the reaction kettle to serve as base solution. And (3) dropwise adding the mixed metal salt solution and the mixed alkali solution into the reaction kettle under the protective atmosphere. Controlling the dropping speed of the mixed alkali to stabilize the PH value within a certain range, and performing coprecipitation reaction to synthesize the precursor. Continuing stirring after the feeding is finished, aging to obtain a precipitate, filtering, washing and vacuum drying the precipitate to obtain a modified high-nickel cobalt-free cathode material precursor;
and (2) adding the modified precursor, lithium salt and a metal salt into a mortar according to a certain proportion, and uniformly mixing and grinding. And under the oxygen atmosphere, the precursor is subjected to two stages of presintering and calcining to obtain the high-entropy alloy modified high-nickel cobalt-free anode material.
For a better understanding of the present invention, reference is made to the following detailed description of the invention taken in conjunction with the accompanying drawings and detailed description. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention. Additionally, endpoints of ranges and any values disclosed herein are not limited to the precise range or value, and such range or value should be understood to encompass values that are close to such range or value. For numerical ranges, the endpoints of each range, and the individual points may be combined with each other to arrive at one or more new numerical ranges, which are to be considered as specifically disclosed herein.
Assembling and testing CR2032 button battery: positive electrode material (final product prepared in comparative example and example), ketjen black: polyvinylidene fluoride (PVDF) in a mass ratio of 90:5.5:4.5 dissolving in N-methyl pyrrolidone (NMP) to prepare slurry, coating the slurry on an aluminum foil, drying, cutting the aluminum foil loaded with active substances into small discs with the diameter of 12mm by a cutting machine, using the small discs for an anode, taking a metal lithium sheet as a cathode, taking polypropylene (PP) as a diaphragm, taking a carbonic acid ester solution with the molar concentration of 1M as an electrolyte (wherein the solvent is ethylene carbonate, diethyl carbonate, methyl ethyl carbonate and LiPF with the volume ratio of 3:2:5 6 ) All cells were assembled in an argon atmosphere glove box.
The assembled CR2032 button battery is tested by adopting a CT2001A LAND battery tester, the current density of 1C is defined to be 180mAh/g, the charging and discharging interval is 2.7-4.4V, and the testing temperature is 25 ℃.
Example 1
In this example, deionized water was added to the reactor by adding 3mol/L ammoniaThe pH was adjusted to 11 with water and 4mol/L sodium hydroxide. Under the protective atmosphere (such as argon), 2mol/L mixed metal salt solution (prepared by mol ratio of Ni to Mn to Ti to Zr to Mg=0.83 to 0.13 to 0.01) of nickel sulfate hexahydrate, manganese sulfate monohydrate, titanyl sulfate, zirconium oxychloride and anhydrous magnesium sulfate is dropwise added into a reaction kettle, the pH value is stabilized at 11 by adjusting the dropping speed of the mixed alkali solution, coprecipitation reaction is carried out, stirring is continued for 2 hours after feeding is finished, precipitate is obtained after aging for 1 hour, and the precipitate is filtered, washed and dried in vacuum to obtain the precursor of the positive electrode material. Precursor and LiOH.H 2 O and calcium chloride are mixed, ground and mixed uniformly, and the precursor and LiOH.H 2 The molar ratio of O to calcium chloride is 1:1.06:0.01. calcining in a tube furnace under oxygen atmosphere, pre-calcining for 5 hours at 450 ℃, then calcining for 17 hours at 780 ℃, wherein the temperature rising rate of the pre-calcining and calcining stages is 5 min/DEG C, and finally cooling to 200 ℃ at the cooling rate of 5 min/DEG C to obtain the high-entropy alloy modified high-nickel cobalt-free cathode material (marked NMCTZM).
The positive electrode material obtained in this example was used to assemble a battery: charging and discharging under 1C multiplying power, wherein the first 1C discharging is 186.9mAh/g, the capacity after 1C circulation for 100 circles is 177.6mAh/g, and the capacity retention rate is 95.1%. Can contribute to a specific capacity of 135.9mAh/g at a high magnification of 20C.
Example 2
In this example, deionized water was added to the reaction vessel, and the pH was adjusted to 11 by adding 3mol/L aqueous ammonia and 4mol/L sodium hydroxide. Under a protective atmosphere (such as argon), 2mol/L mixed metal salt solution (prepared by mol ratio of Ni: mn: mo: fe: V=0.83: 0.13: 0.01) of nickel sulfate hexahydrate, manganese sulfate monohydrate, ammonium molybdate, ferric sulfate hydrate and vanadyl sulfate is dropwise added into a reaction kettle, the pH value is stabilized at 11 by adjusting the dropping speed of the mixed alkali solution, coprecipitation reaction is carried out, stirring is continued for 2 hours after feeding is finished, ageing is carried out for 1 hour to obtain precipitate, and the precipitate is filtered, washed and dried in vacuum to obtain a positive electrode material precursor. Precursor and LiOH.H 2 O and lanthanum nitrate hydrate are ground and mixed uniformly, and the precursor and LiOH.H 2 The molar ratio of O to lanthanum nitrate hydrate is 1:1.06:0.01. in a tube under an oxygen atmosphereCalcining in a furnace for 5 hours at 450 ℃, then calcining for 17 hours at 780 ℃, wherein the temperature rising rate of the pre-calcining and calcining stages is 5 min/DEG C, and finally cooling to 200 ℃ at the cooling rate of 5 min/DEG C to obtain the high-entropy alloy modified high-nickel cobalt-free cathode material (marked NMLMFV).
The positive electrode material obtained in this example was used to assemble a battery: charging and discharging under the 1C multiplying power, wherein the first 1C discharging is 182.6mAh/g, the capacity after 1C circulation for 100 circles is 176.1mAh/g, and the capacity retention rate is 96.4%. Can contribute 89.1mAh/g specific capacity at high magnification of 20C.
Example 3
In this example, deionized water was added to the reaction vessel, and the pH was adjusted to 11 by adding 3mol/L aqueous ammonia and 4mol/L sodium hydroxide. Under a protective atmosphere (such as argon), dropwise adding a mixed metal salt solution of 2mol/L nickel sulfate hexahydrate, manganese sulfate monohydrate and cobalt sulfate heptahydrate (prepared by mol ratio of Ni to Mn to Co=0.83 to 0.13 to 0.04) into a reaction kettle, stabilizing the pH value at 11 by regulating the dropping speed of a mixed alkali solution, performing coprecipitation reaction, continuously stirring for 2 hours after feeding, aging for 1 hour to obtain a precipitate, and filtering, washing and vacuum drying the precipitate to obtain a positive electrode material precursor. Precursor and LiOH.H 2 O is ground and mixed uniformly, and the precursor and LiOH H 2 The molar ratio of O is 1:1.05. calcining in a tube furnace under the oxygen atmosphere, firstly presintering for 5 hours at 450 ℃, then calcining for 17 hours at 780 ℃, wherein the temperature rising rate of the presintering and calcining stages is 5 min/DEG C, and finally cooling to 200 ℃ at the cooling rate of 5 min/DEG C to obtain the high-entropy alloy modified high-nickel positive electrode material (marked NMC).
The positive electrode material obtained in this example was used to assemble a battery: charging and discharging under 1C multiplying power, wherein the first 1C discharging is 193.15mAh/g, the capacity after 1C circulation for 100 circles is 119.01mAh/g, and the capacity retention rate is 61.6%. Can contribute a specific capacity of 56.2mAh/g at a high magnification of 20C.
Example 4
In this example, deionized water was added to the reaction vessel, and the pH was adjusted to 11 by adding 3mol/L aqueous ammonia and 4mol/L sodium hydroxide. Dropwise adding the mixture into a reaction kettle under a protective atmosphere (such as argon)2mol/L mixed metal salt solution of nickel sulfate hexahydrate and manganese sulfate monohydrate (prepared by the mol ratio of Ni to Mn=0.83:0.17), stabilizing the pH value at 11 by adjusting the dropping speed of the mixed alkali solution, performing coprecipitation reaction, continuously stirring for 2 hours after feeding is finished, aging for 1 hour to obtain a precipitate, filtering, washing and vacuum drying the precipitate to obtain a positive electrode material precursor. Precursor and LiOH.H 2 O is ground and mixed uniformly, and the precursor and LiOH H 2 The molar ratio of O is 1:1.05. calcining in a tube furnace under oxygen atmosphere, firstly presintering for 5 hours at 450 ℃, then calcining for 17 hours at 780 ℃, wherein the temperature rising rate of the presintering and calcining stages is 5 min/DEG C, and finally cooling to 200 ℃ at the cooling rate of 5 min/DEG C to obtain the high-entropy alloy modified high-nickel cobalt-free positive electrode material (marked NM).
The positive electrode material obtained in this example was used to assemble a battery: charging and discharging under the 1C multiplying power, wherein the first 1C discharging is 152.1mAh/g, the capacity after 1C circulation for 100 circles is 129.5mAh/g, and the capacity retention rate is 85.1%. Can contribute a specific capacity of 1.2mAh/g at a high magnification of 20C.
As shown in FIG. 1, the X-ray diffraction patterns (XRD) of the final product positive electrode materials prepared in examples 1 to 4 show that the high-entropy alloy modification does not change the crystal structure of the materials, and all the materials after modification still remainSpace group.
As shown in fig. 2, scanning Electron Microscope (SEM) pictures of the final product cathode materials prepared in examples 1 to 4, it can be seen from fig. 2 that the primary particles of the cathode material modified by the high-entropy alloy are changed from rod shape to block shape. Illustrating the growth of the a-axis and the b-axis.
As shown in fig. 3, the end product prepared in example 1 was subjected to a spectral test surface scan (EDS), and as can be seen in fig. 3, the selected metal elements were successfully doped.
As shown in fig. 4, the end product prepared in example 2 was subjected to a spectral test surface scan (EDS), and as can be seen in fig. 4, the selected metal elements were successfully doped.
As shown in fig. 5, the charge-discharge electrochemical performance diagrams of the assembled batteries in examples 1 to 4 at different multiplying powers under 2.7 to 4.4V show that the multiplying power performance of the final products prepared in examples 1 and 2 is obviously improved in fig. 5, which illustrates that the high entropy modification plays an important role in improving the multiplying power performance of the cobalt-free positive electrode.
As shown in fig. 6, the electrochemical performance diagrams of the assembled batteries in examples 1 to 4 at the 1C rate charge-discharge cycle at 2.7 to 4.4V show that the cycle performance of the final products prepared in examples 1 and 2 is obviously improved in fig. 6, which illustrates that the high entropy modification plays an important role in improving the long cycle performance of the cobalt-free positive electrode.
The implementation result shows that the high-entropy alloy modified high-nickel cobalt-free positive electrode material has more stable structure and increased lithium ion migration rate, and the obtained material has excellent high-rate performance and cycle stability. The positive electrode material obtained by the invention is assembled into a battery, and the performance indexes are as follows: charging and discharging under the 1C multiplying power, wherein the first 1C discharging can reach more than 186mAh/g, the capacity can reach more than 177mAh/g after 1C circulation for 100 circles, and the capacity retention rate can reach more than 90%. Can contribute to the specific capacity of more than 135mAh/g under the high multiplying power of 20C. The invention has simple process flow, does not change the original industrialized synthetic route and is easy to realize industrialization.
Claims (9)
1. A high-entropy alloy modified high-nickel cobalt-free positive electrode material is characterized in that the chemical formula of the high-nickel cobalt-free positive electrode material is LiNi x Mn y TM (1-x-y)/4 TM (1-x-y)/4 TM (1-x-y)/4 TM (1-x-y)/4 O 2 ，0.8<x<1，0<y<0.2，0<x+y<1, tm are each one of transition metal elements.
2. The method for preparing the high-entropy alloy modified high-nickel cobalt-free positive electrode material according to claim 1, wherein nickel ions, manganese ions and three transition metal ions are doped into a precursor through a coprecipitation method, and then lithium salt and a fourth transition metal salt are mixed with the precursor to be sintered together, so that the high-entropy alloy modified high-nickel cobalt-free positive electrode material is obtained.
3. The method for preparing the high-entropy alloy modified high-nickel cobalt-free positive electrode material according to claim 2, which is characterized by comprising the following steps:
step (1): taking water as a solution, taking a mixed alkali solution of ammonia water and sodium hydroxide as a complexing agent and a precipitator, dropwise adding a mixed metal salt solution prepared from five metal salts, and obtaining a high-entropy alloy modified high-nickel cobalt-free positive electrode material precursor by a coprecipitation method;
step (2): and mixing the precursor, the lithium salt and the metal salt in a mortar, calcining under oxygen, pre-calcining at a lower temperature, and then calcining at an elevated temperature to obtain the high-entropy alloy modified high-nickel cobalt-free anode material after the sintering process is completed.
4. The method for preparing the high-entropy alloy modified high-nickel cobalt-free cathode material according to claim 3, wherein in the step (1), five mixed metal salt solutions are mixed aqueous solutions of three of nickel sulfate hexahydrate and manganese sulfate monohydrate, and ferric sulfate hydrate, cobalt sulfate heptahydrate, lanthanum nitrate hydrate, titanyl sulfate, zirconium oxychloride, magnesium sulfate, vanadyl sulfate, anhydrous calcium chloride and ammonium molybdate, wherein the total concentration of metal ions in the mixed metal salt solutions is 1-3 mol/L.
5. The method for preparing a high-entropy alloy modified high-nickel cobalt-free positive electrode material according to claim 4, wherein in the step (2), the precursor: lithium salt: the mole ratio of the fourth transition metal salt is 1:1.02-1.08:0.005-0.015, and the fourth transition metal salt is one of hydrated lanthanum nitrate, titanyl sulfate, zirconium oxychloride, magnesium sulfate and anhydrous calcium chloride.
6. The method for preparing the high-entropy alloy modified high-nickel cobalt-free cathode material according to claim 3, wherein the molar ratio of nickel, manganese and the remaining four transition metal salts is x: y: (1-x-y)/4: (1-x-y)/4: (1-x-y)/4: (1-x-y)/4, 0.8< x <1,0< y <0.2,0< x+y <1.
7. The method for preparing a high-entropy alloy modified high-nickel cobalt-free positive electrode material according to claim 3, wherein in the step (2), the pre-sintering temperature is 400-500 ℃ and the pre-sintering time is 4-6 hours.
8. The method for preparing a high-entropy alloy modified high-nickel cobalt-free cathode material according to claim 3, wherein in the step (2), the calcination temperature is 750-830 ℃ and the sintering time is 10-20 hours.
9. The method for preparing a high-entropy alloy modified high-nickel cobalt-free cathode material according to claim 3, wherein in the step (1), the mixed alkali solution consists of 1 to 4mol/L sodium hydroxide solution and 1.5 to 5mol/L ammonia water solution, and the pH value is adjusted and stabilized to 10 to 12 by the mixed alkali solution.
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