CN114709410A - Preparation method of layered quaternary cobalt-free monocrystal precursor and anode material - Google Patents
Preparation method of layered quaternary cobalt-free monocrystal precursor and anode material Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 45
- 239000010405 anode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 67
- 239000011572 manganese Substances 0.000 claims abstract description 36
- 239000010406 cathode material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910013100 LiNix Inorganic materials 0.000 claims abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 21
- 239000012266 salt solution Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 238000000975 co-precipitation Methods 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 14
- 239000008139 complexing agent Substances 0.000 claims description 12
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 11
- 239000012716 precipitator Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011268 mixed slurry Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229940099596 manganese sulfate Drugs 0.000 claims description 8
- 239000011702 manganese sulphate Substances 0.000 claims description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- 229910013716 LiNi Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- ZFQCFWRSIBGRFL-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;zirconium(4+) Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZFQCFWRSIBGRFL-UHFFFAOYSA-B 0.000 claims description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229960001759 cerium oxalate Drugs 0.000 claims description 2
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 5
- -1 nickel manganese cerium zirconium hydroxide Chemical compound 0.000 abstract description 5
- 239000011258 core-shell material Substances 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 241001674048 Phthiraptera Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A preparation method of a layered quaternary cobalt-free single crystal precursor and a cathode material comprises the following steps: the chemical formula of the layered single crystal precursor is NixMnyCemZrn(OH)2The chemical formula of the single crystal anode material is LiNixMnyCemZrnO2Wherein x is more than or equal to 0.5<1，0<y≤0.2，0<m≤0.2，0<n is less than or equal to 0.1, and x + y + m + n is 1. The invention adopts the mature precursor preparation process in industry to prepare the layered quaternary cobalt-free single crystal precursor. Then, the layered quaternary cobalt-free single crystal anode material is synthesized by a segmented high-temperature method. The layered quaternary precursor is composed of nickel manganese hydroxide with the inner diameter of 3-4 mu m and nickel manganese cerium zirconium hydroxide with the outer diameter of 1-1.5 mu m, is different from a core-shell structure in academia and industry, and is internally compact. The compact layered structure and the element coordination of the invention improve the stability of the whole single crystal material in bulk phaseAnd on the other hand, the coordination effect among elements is exerted, the side reaction is effectively reduced by the cerium and the zirconium on the outer layer, the side effect caused by no cobalt is reduced, and the stability and the electrochemical performance of the single crystal material are further improved.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, mainly relates to a lithium ion battery anode material precursor and a preparation method of an anode material, and particularly relates to a layered structure quaternary nickel-manganese-cerium-zirconium cobalt-free single crystal ternary anode material precursor and a preparation method of an anode material.
Background
Due to the rapid development of electric vehicles, people put higher requirements on the energy density of Lithium Ion Batteries (LIBs), and therefore, the nickel-rich layered oxide is expected to become a cathode material of the next generation of lithium ion batteries of electric vehicles. When the Ni content in the layered positive electrode is increased, structural instability caused by anisotropic lattice shrinkage in a deep charge state may generate local stress concentration along grain boundaries and develop into microcracks, so that the electrolyte penetrates and erodes the interior of secondary particles, resulting in severe side reactions. The appearance of the single crystal anode material greatly improves the generation of microcracks, well reduces side reactions and greatly improves the electrochemical performance and the thermal stability.
Although the single crystal anode material has higher crack resistance than the polycrystalline anode material, the single crystal material cracks inside the single crystal through the sliding of the plane of the trigger layer in the circulation process, and the structural nonuniformity of the single crystal material can cause nonuniform stress, thereby causing structural defects and limiting Li+Diffusion kinetics, ultimately leading to capacity fade. In addition, at present, cobalt is a scarce resource in the world, and the bottleneck of global supply of cobalt resources has caused a hindrance to further development of lithium ion batteries, and this hindrance has further expanded with the passage of time, so that this situation has prompted researchers' research on cobalt-free cathode materials. However, cobalt has significant advantages in the layered oxide cathode material, such as reduction of lithium-nickel mixed-row, stabilization of the layered structure, and the like, and the cobalt-free oxide cathode material causes structural instability, thereby causing cycle performance degradation of the cathode material.
Under these combined factors, numerous researchers have modified the defects of single crystal positive electrode materials. Such as common bulk phase doping and surface coating, but the modification methods solve some problems more or less, but doping easily causes reduction of battery capacity, and coating modification has the problem of nonuniform coating.
Therefore, the patent discloses a layered structure quaternary nickel-manganese-cerium-zirconium cobalt-free single crystal precursor and a preparation method of an anode material, and the patent does not adopt a conventional modification method, but directly synthesizes a target product layered structure quaternary cobalt-free single crystal precursor at a precursor stage, and simultaneously synthesizes the layered structure cobalt-free single crystal ternary anode material by adopting a pre-sintering-extremely high temperature-high temperature three-stage calcination method, so that the cobalt-free single crystal anode material has excellent electrochemical performance, better multiplying power performance and stronger mechanical strain resistance.
Disclosure of Invention
The technical problem solved by the invention is as follows: the layered quaternary cobalt-free single crystal precursor and the anode material are prepared by adopting a twice coprecipitation method and a pre-sintering-extremely high temperature-high temperature segmented calcination method, on one hand, the preparation method is simple and easy to industrialize, on the other hand, the structural design of the single crystal is achieved through the structural design of the precursor, and the structural design of the single crystal is better than the structural design of a core-shell structure and the like of the anode material in the academic and industrial fields at present, so that the structural performance of the single crystal is improved, and the cyclic stability of the cobalt-free material is improved.
The technical scheme adopted by the invention for solving the technical problems is that a preparation method of a layered quaternary cobalt-free single crystal precursor and a cathode material comprises the following steps: the chemical formula of the layered single crystal precursor is NixMnyCemZrn(OH)2The chemical formula of the single crystal anode material is LiNixMnyCemZrnO2. Wherein x is more than or equal to 0.5<1，0<y≤0.2，0<m≤0.2，0<n≤0.1，x+y+m+n＝1。
The layered quaternary cobalt-free single crystal precursor and the positive electrode material of claim 1, wherein the layered quaternary precursor is composed of nickel manganese hydroxide with an inner diameter of 3-4 μm and nickel manganese cerium zirconium hydroxide with an outer diameter of 0.5-1 μm, and the positive electrode material is composed of LiNi with an inner diameter of 3-4 μmxMnyO2And LiNi of 0.5 to 1 μm outsidexMnyCemZrnO2The composition is still compact particles inside the material.
The invention further solves the technical problem by adopting the technical scheme that the preparation method of the layered quaternary cobalt-free single crystal anode material comprises the following steps: the preparation method of the layered quaternary cobalt-free single crystal precursor is characterized by comprising the following steps of:
(1) uniformly mixing soluble salts of Ni and Mn with a certain molar ratio in pure water to obtain a mixed salt solution A; uniformly mixing soluble salts of Ni, Mn, Ce and Zr in a certain molar ratio in pure water to obtain a mixed salt solution B;
(2) mixing the mixed salt solution A obtained in the step (1), a precipitator NaOH solution with a certain concentration and a complexing agent NH3·H2Adding the O solution into a reaction kettle together, carrying out coprecipitation reaction, continuously stirring, and reacting for a period of time to obtain solid-liquid mixed slurry NixMny(OH)2The feed was stopped.
(3) Adding the mixed salt solution B obtained in the step (1) into the slurry obtained in the step (2), and simultaneously adjusting a precipitator NaOH solution and a complexing agent NH3·H2Adding O solution, carrying out secondary coprecipitation reaction, continuously stirring to obtain solid-liquid mixed slurry, washing the slurry, filtering, drying, demagnetizing and the like to obtain the layered quaternary cobalt-free single crystal precursor NixMnyCemZrn(OH)2。
The preparation method of the layered quaternary cobalt-free single crystal anode material is characterized by comprising the following steps of:
weighing a certain proportion of lithium source, and mixing the lithium source with the precursor Ni obtained in the step (3) of claim 3xMnyCemZrn(OH)2Uniformly mixing, and sintering at high temperature in sections to obtain the layered quaternary cobalt-free single crystal anode material.
Further, in the step (1), the nickel source is one or more of nickel acetate, nickel nitrate and nickel sulfate; the manganese source is one or more of manganese acetate, manganese nitrate and manganese sulfate; the zirconium source is one or more of zirconium acetate, zirconium citrate, zirconium nitrate and zirconium sulfate; the cerium source is one or more of cerium acetate, cerium oxalate, cerium nitrate and cerium sulfate.
Further, in the step (1), the concentration of the mixed solution A is 2-8 mol/L; the concentration of the mixed solution B in the step (1) is 2-4 mol/L; in the steps (2) and (3), the concentration of the precipitator NaOH solution is 5-12mol/L, and the complexing agent NH3·H2The concentration of the O solution is 6-10 mol/L.
Further, in the step (2), the stirring speed of the coprecipitation reaction is 350-600rpm, the pH value of the reaction solution is 10.5-13.5, the ammonia value is 10-20g/L, the reaction temperature is 60-85 ℃, and the atmosphere of the reaction kettle is one or more of nitrogen and argon.
Further, in claim 4, the lithium source is one or more of lithium hydroxide, lithium carbonate and lithium nitrate; the ratio of the lithium source to the precursor is Li: and TM is (1.03-1.25): 1 and is the molar ratio of lithium to metal.
Further, in claim 4, the calcination treatment procedure is three-stage calcination treatment, the first stage calcination temperature is 450-; the second stage calcination temperature is 850-1000 ℃, and the temperature is kept for 3-8 h; the third stage calcination temperature is 650-950 ℃, and the temperature is kept for 9-16 h. The calcining atmosphere in the step is one of air, oxygen-enriched air and pure oxygen.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts the highly mature coprecipitation method and high-temperature sintering method in industry to prepare the quaternary nickel-manganese-cerium-zirconium cobalt-free single crystal precursor and the positive electrode material with the layered structure, the layered structure not only slows down the corrosion speed of electrolyte to the cobalt-free single crystal positive electrode material in the charging and discharging process, but also improves the structural stability, the conductivity and the ion transmission rate of the cobalt-free single crystal positive electrode material;
(2) the layered structure single crystal cobalt-free anode material is different from a conventional core-shell structure and coating modification, compared with the core-shell structure, the inner part of two layers of materials of the layered structure is compact, side reaction can be slowed down better, and the layered structure can be maintained better, and compared with the surface coating modification, the layered structure single crystal material has LiCE with micron-sized thicknessmZrnO2Has better protective performance than coating modification and is coatedThis is not the case for a layered structure as regards inhomogeneities. Meanwhile, the single crystal anode material does not need to be additionally modified, and the preparation method can be used for preparing the anode material in the normal anode production process, and is convenient and easy for industrial production.
(3) As researches show that the valence of Zr and Ce elements in the anode material is stable, the stability of the structure of the layered anode material can be effectively maintained, the Zr element also has excellent metal strength and thermal stability, the mechanical strength and the thermal stability of the anode material can be enhanced, and the Zr element and the Ce element are used for replacing the cobalt element in the anode material, so that the production cost of the anode material is reduced;
(4) the invention provides a layered quaternary cobalt-free single crystal precursor, a preparation method of a positive electrode material and a synthesis strategy, which can obviously improve the structural stability of the material through the synergistic effect of a plurality of elements, realize good battery cycle performance and enhance the structural stability and the electric conductivity of the material. The preparation method provided by the invention has the advantages of simple process, low cost, stable performance and obvious modification on the electrochemical performance.
Drawings
FIG. 1 is an SEM image of a layered quaternary cobalt-free single crystal precursor prepared according to example 1 of the present invention;
FIG. 2 is an SEM image of a layered quaternary cobalt-free single-crystal positive electrode material prepared in example 1 of the present invention;
fig. 3 is an XRD pattern of the layered quaternary cobalt-free single-crystal positive electrode material prepared in example 1 of the present invention;
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
The chemical formula of the layered quaternary cobalt-free single crystal cathode material of the embodiment is LiNi0.90Mn0.06Ce0.01Zr0.03O2。
The preparation method of the layered quaternary cobalt-free single crystal cathode material of the embodiment comprises the following steps:
(1) adding nickel sulfate and manganese sulfate into deionized water according to the mol ratio of 0.93:0.07, and uniformly stirring to prepare a mixed salt solution A with the concentration of 4 mol/L; adding nickel sulfate, manganese sulfate, cerium sulfate and zirconium sulfate into deionized water according to the mol ratio of 0.88:0.06:0.02:0.04, and uniformly stirring to prepare a mixed salt solution B of 4 mol/L;
(2) mixing the mixed salt solution A obtained in the step (1), 6mol/L of precipitator NaOH solution and 8mol/L of complexing agent NH3·H2Adding the O solution into a reaction kettle together for coprecipitation reaction, continuously stirring at the speed of 350rpm, controlling the temperature of the reaction kettle to be 70 ℃, controlling the ammonia value of reaction liquid to be 10g/L and the pH value to be about 12.5, and reacting for 20 hours by a coprecipitation method to obtain solid-liquid mixed slurry Ni0.88Mn0.06(OH)2。
(3) Adding the mixed salt solution B obtained in the step (2) into the slurry obtained in the step (2), and simultaneously adjusting a precipitator NaOH solution and a complexing agent NH3·H2Adding O solution, carrying out secondary coprecipitation reaction, continuously stirring to obtain solid-liquid mixed slurry, washing the slurry, filtering, drying, demagnetizing and the like to obtain the layered quaternary cobalt-free single crystal precursor Ni0.90Mn0.06Ce0.01Zr0.03(OH)2。
(4) According to a molar ratio of Li: weighing a certain proportion of lithium source in TM-1.05: 1, and mixing the lithium source with the precursor Ni obtained in the step (3)0.88Mn0.06Ce0.02Zr0.04(OH)2Uniformly mixing, sintering at high temperature in stages, calcining at 480 ℃ for 5h in pure oxygen atmosphere, then heating to 860 ℃ for 5h, then cooling to 780 ℃ for 12h, and finally naturally cooling to obtain the layered quaternary cobalt-free single crystal anode material LiNi0.90Mn0.06Ce0.01Zr0.03O2。
The single crystal precursor and the positive electrode material of the product of this example were scanned by a scanning electron microscope, and the results are shown in fig. 1 and fig. 2, which are precursor particles and single crystal particles of about 3 μm.
The product of this example was analyzed by X-ray powder diffraction, and the result is shown in FIG. 3, which shows that LiNi was synthesized0.90Mn0.06Ce0.01Zr0.03O2Is a single phase, the material being a typical hexagonal layerThe structure of the structure belongs to the R-3m space group.
The layered quaternary cobalt-free single crystal cathode material LiNi of the embodiment is adopted0.90Mn0.06Ce0.01Zr0.03O2The prepared positive electrode is assembled into a button battery, electrochemical performance test is carried out, the first discharge gram capacity of 0.1C (1C is 200mA/g) is within the voltage range of 3-4.3V at 25 ℃, the 1C discharge specific capacity is up to 221.1mAh/g, the 1C discharge specific capacity is 202.3mAh/g, and the capacity retention rate is up to 91.5% after 100 cycles of circulation.
Example 2
The chemical formula of the layered quaternary cobalt-free single crystal cathode material in the embodiment is LiNi0.83Mn0.10Ce0.03Zr0.04O2。
The preparation method of the layered quaternary cobalt-free single crystal cathode material of the embodiment comprises the following steps:
(1) adding nickel sulfate and manganese sulfate into deionized water according to the mol ratio of 0.9:0.1, and uniformly stirring to prepare a mixed salt solution A with the concentration of 6 mol/L; adding nickel sulfate, manganese sulfate, cerium sulfate and zirconium sulfate into deionized water according to the mol ratio of 0.8:0.09:0.05:0.06, and uniformly stirring to prepare a mixed salt solution B of 6 mol/L;
(2) mixing the mixed salt solution A obtained in the step (1), 6mol/L of precipitator NaOH solution and 8mol/L of complexing agent NH3·H2Adding the O solution into a reaction kettle together for coprecipitation reaction, continuously stirring at the speed of 350rpm, controlling the temperature of the reaction kettle to be 65 ℃, controlling the ammonia value of reaction liquid to be 15g/L and the pH value to be about 12.5, and reacting for 18 hours by a coprecipitation method to obtain solid-liquid mixed slurry Ni0.8Mn0.1(OH)2。
(3) Adding the mixed salt solution B obtained in the step (2) into the slurry obtained in the step (2), and simultaneously adjusting a precipitator NaOH solution and a complexing agent NH3·H2Adding O solution, carrying out secondary coprecipitation reaction, continuously stirring to obtain solid-liquid mixed slurry, washing the slurry, filtering, drying, demagnetizing and the like to obtain the layered quaternary cobalt-free single crystal precursor Ni0.83Mn0.10Ce0.03Zr0.04(OH)2。
(4) According to a molar ratio of Li: weighing a certain proportion of lithium source in TM 1.04:1, and mixing the lithium source with the precursor Ni obtained in the step (3)0.83Mn0.10Ce0.03Zr0.04(OH)2Uniformly mixing, sintering at high temperature in stages, calcining at 480 ℃ for 5h in pure oxygen atmosphere, then heating to 900 ℃ for calcining for 6h, then cooling to 810 ℃ for calcining for 15h, and finally naturally cooling to obtain the layered quaternary cobalt-free single crystal anode material LiNi0.83Mn0.10Ce0.03Zr0.04O2。
The layered quaternary cobalt-free single crystal cathode material LiNi of the embodiment is adopted0.83Mn0.10Ce0.03Zr0.04O2The prepared positive electrode is assembled into a button battery, electrochemical performance test is carried out, the first discharge gram capacity of 0.1C (1C is 200mA/g) is within the voltage range of 3-4.3V at 25 ℃, the first discharge gram capacity is 215.3mAh/g, the discharge specific capacity at 1C is 197.4mAh/g, and the capacity retention rate is 92.9% after 100 cycles.
Example 3
The chemical formula of the layered quaternary cobalt-free single crystal cathode material of the embodiment is LiNi0.65Mn0.20Ce0.06Zr0.09O2。
The preparation method of the layered quaternary cobalt-free single crystal cathode material of the embodiment comprises the following steps:
(1) adding nickel sulfate and manganese sulfate into deionized water according to the mol ratio of 0.75:0.25, and uniformly stirring to prepare a mixed salt solution A with the concentration of 6 mol/L; adding nickel sulfate, manganese sulfate, cerium sulfate and zirconium sulfate into deionized water according to the molar ratio of 0.6:0.15:0.1:0.15, and uniformly stirring to prepare a mixed salt solution B of 6 mol/L;
(2) mixing the mixed salt solution A obtained in the step (1), 6mol/L of precipitator NaOH solution and 8mol/L of complexing agent NH3·H2Adding the O solution into a reaction kettle together for coprecipitation reaction, continuously stirring at the speed of 350rpm, controlling the temperature of the reaction kettle to be 75 ℃, controlling the ammonia value of reaction liquid to be 14g/L and the pH value to be about 12.6, and reacting for 16 hours by a coprecipitation method to obtain solid-liquid mixed slurry Ni0.75Mn0.25(OH)2。
(3) Adding the mixed salt solution B obtained in the step (2) into the slurry obtained in the step (2), and simultaneously adjusting a precipitator NaOH solution and a complexing agent NH3·H2Adding O solution, carrying out secondary coprecipitation reaction, continuously stirring to obtain solid-liquid mixed slurry, washing the slurry, filtering, drying, demagnetizing and the like to obtain the layered quaternary cobalt-free single crystal precursor Ni0.65Mn0.20Ce0.06Zr0.09(OH)2。
(4) According to a molar ratio of Li: weighing a certain proportion of lithium source in TM-1.03: 1, and mixing the lithium source with the precursor Ni obtained in the step (3)0.65Mn0.20Ce0.06Zr0.09(OH)2Uniformly mixing, sintering at high temperature in stages, calcining at 450 ℃ for 6h in pure oxygen atmosphere, then heating to 970 ℃ for 3h, then cooling to 880 ℃ for 15h, and finally naturally cooling to obtain the layered quaternary cobalt-free single crystal positive electrode material LiNi0.65Mn0.20Ce0.06Zr0.09O2。
The layered quaternary cobalt-free single crystal cathode material Li Ni of the embodiment is adopted0.65Mn0.20Ce0.06Zr0.09O2The prepared positive electrode is assembled into a button battery, electrochemical performance test is carried out, the first discharge gram capacity under 0.1C (1C is 200mA/g) multiplying power reaches 180.7mAh/g, the 1C discharge specific capacity reaches 165.4mAh/g, and the capacity retention rate reaches 95.3% after 100 cycles of circulation at 25 ℃ in a voltage range of 3-4.3V.
Claims (9)
1. A preparation method of a layered quaternary cobalt-free single crystal precursor and a cathode material comprises the following steps: the chemical formula of the layered single crystal precursor is NixMnyCemZrn(OH)2The chemical formula of the single crystal anode material is LiNixMnyCemZrnO2Wherein x is more than or equal to 0.5<1，0<y≤0.2，0<m≤0.2，0<n≤0.1，x+y+m+n＝1。
2. The layered quaternary cobalt-free single crystal precursor and positive electrode material according to claim 1, wherein the layered quaternary cobalt-free single crystal precursor is layered quaternaryThe element precursor is composed of Ni with the inner part of 3-4 mu mxMny(OH)2And Ni of 1 to 1.5 μm outsidexMnyCemZrn(OH)2The positive electrode material consists of LiNi with the inner part of 3-4 mu mxMnyO2And LiNi of 1 to 1.5 μm outsidexMnyCemZrnO2The composition is still compact particles inside the material.
3. A method of preparing a layered quaternary cobalt-free single crystal precursor according to claim 1, comprising the steps of:
(1) uniformly mixing soluble salts of Ni and Mn with a certain molar ratio in pure water to obtain a mixed salt solution A; uniformly mixing soluble salts of Ni, Mn, Ce and Zr in a certain molar ratio in pure water to obtain a mixed salt solution B;
(2) mixing the mixed salt solution A obtained in the step (1), a precipitator NaOH solution with a certain concentration and a complexing agent NH3·H2Adding the O solution into a reaction kettle together, carrying out coprecipitation reaction, continuously stirring, and reacting for a period of time to obtain solid-liquid mixed slurry NixMny(OH)2The feed was stopped.
(3) Adding the mixed salt solution B obtained in the step (1) into the slurry obtained in the step (2), and simultaneously adjusting a precipitator NaOH solution and a complexing agent NH3·H2Adding O solution, carrying out secondary coprecipitation reaction, continuously stirring to obtain solid-liquid mixed slurry, washing the slurry, filtering, drying, demagnetizing and the like to obtain the layered quaternary cobalt-free single crystal precursor NixMnyCemZrn(OH)2。
4. A method for preparing a layered quaternary cobalt-free single crystal positive electrode material according to claim 1, comprising the steps of:
weighing a certain proportion of lithium source, and mixing the lithium source with the precursor Ni obtained in the step (3) in the claim 3xMnyCemZrn(OH)2Mixing uniformly, and performing pre-treatmentSintering at high temperature by a three-section sintering method of sintering-extremely high temperature-high temperature to obtain the layered quaternary cobalt-free single crystal anode material.
5. The preparation method of the dual modified low-zirconium ternary cathode material precursor according to claim 3, wherein the nickel source is one or more of nickel acetate, nickel nitrate and nickel sulfate; the manganese source is one or more of manganese acetate, manganese nitrate and manganese sulfate; the zirconium source is one or more of zirconium acetate, zirconium citrate, zirconium nitrate and zirconium sulfate; the cerium source is one or more of cerium acetate, cerium oxalate, cerium nitrate and cerium sulfate.
6. The preparation method of the double-modified low-cobalt ternary cathode material precursor as claimed in claim 3, wherein the concentration of the mixed solution A in the step (1) is 2-8 mol/L; the concentration of the mixed solution B in the step (1) is 2-4 mol/L; in the steps (2) and (3), the concentration of the precipitant NaOH solution is 5-12mol/L, and the concentration of the complexing agent NH 3. H2O solution is 6-10 mol/L.
7. The preparation method of the dual modified low-cobalt ternary cathode material precursor as claimed in claim 3, wherein in the step (2), the stirring speed of the coprecipitation reaction is 350-600rpm, the pH value of the reaction solution is 10.5-13.5, the ammonia value is 12-17g/L, the reaction temperature is 60-85 ℃, and the atmosphere in the reaction kettle is one or more of nitrogen and argon.
8. The method for preparing the sodium-ion battery multi-element cathode material as recited in claim 4, wherein the lithium source is one or more of lithium hydroxide, lithium carbonate and lithium nitrate; the ratio of the lithium source to the precursor is Li: and TM is (1.03-1.25): 1 and is the molar ratio of lithium to metal.
9. The calcination treatment procedure in the step is pre-sintering-extremely high temperature-high temperature three-stage calcination treatment, the first stage calcination temperature is 450-600 ℃, and the temperature is kept for 4-8 hours; the second stage calcination temperature is 850-1000 ℃, and the temperature is kept for 3-8 h; the third stage calcination temperature is 650-950 ℃, and the temperature is kept for 9-16 h. The calcining atmosphere in the step is one of air, oxygen-enriched air and pure oxygen.
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