CN112079398A - Preparation method and application of gradient composite doped lithium-rich manganese-based material - Google Patents
Preparation method and application of gradient composite doped lithium-rich manganese-based material Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 70
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 60
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000007774 positive electrode material Substances 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 238000005253 cladding Methods 0.000 claims abstract description 3
- 239000002105 nanoparticle Substances 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 239000002002 slurry Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 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
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000000725 suspension Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 241000080590 Niso Species 0.000 description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 238000012958 reprocessing Methods 0.000 description 5
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910009973 Ti2O3 Inorganic materials 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 208000019901 Anxiety disease Diseases 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 230000036506 anxiety Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 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
- 238000004519 manufacturing process Methods 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 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
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
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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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- 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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- 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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Abstract
The invention relates to the technical field of lithium ion battery anode materials and battery preparation, in particular to a novel cobalt-free anode lithium-rich manganese-based material and a modified preparation method thereof. The invention relates to a preparation method of a gradient composite doped lithium-rich manganese-based material, which comprises the following steps: (1) preparing doped lithium hydroxy nickelate nanoparticles: the preparation method comprises the following steps of (1) reacting an oxidant and a nickel source solution with lithium hydroxide in a reaction kettle under certain conditions to prepare the lithium-ion battery; (2) preparing the lithium-rich manganese-based material by secondary doping and cladding: doping and coating the concentrated slurry obtained in the step one under a certain condition by adopting a manganese source, a doped metal ion and a lithium source; (3) drying and sintering the lithium-rich manganese-based material: and drying and sintering the centrifugally separated lithium-rich manganese-based material precursor. The invention aims to provide a preparation method and application of a lithium-rich manganese-based positive electrode material which has high specific capacity, low price, excellent performance, relatively stable structure and high safety.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials and battery preparation, in particular to a novel cobalt-free anode lithium-rich manganese-based material and a modified preparation method thereof.
Background
In the new energy power lithium battery industry, the ternary battery has high energy density originally, can effectively solve the mileage anxiety of private car users, and becomes a mainstream scheme of global new energy passenger cars. However, frequent battery auto-ignition events, and their high production costs, have caused the new energy industry to begin to lose patience with him. But it will certainly be a slow and great project to thoroughly solve the mileage and safety anxiety of users to the electric vehicle. However, although the technology of lithium iron phosphate is advanced, the cruising ability of the whole vehicle cannot be really solved.
The lithium-rich manganese-based anode material has absolute advantages in specific discharge capacity (2 times that of lithium iron phosphate), and has the advantages of low production cost, no toxicity, safety and the like, so that the use requirements of the lithium battery in the fields of small-sized electronic products, electric automobiles and the like can be met.
In order to promote the practical application of the lithium-rich manganese-based positive electrode material to the lithium ion battery, the defects of low coulombic efficiency, rapid platform voltage drop in the discharging process and the like need to be solved from the material direction. Research shows that the mixed exclusion of transition cations in the material can reduce the instability of the material structure, and is one of the main reasons of the defects of the lithium-rich manganese-based positive electrode material. The traditional solid phase method for synthesizing the lithium-rich manganese-based cathode material has the defects that part of raw materials are not uniformly mixed due to large mixing scale of the raw materials, and the cation mixing degree is improved, so that the electrical property of the material is poor. The reported sol-gel method has the same performance, but has higher difficulty in the aspect of promoting the industrial production. The cation mixing and discharging produced by the coprecipitation method are not easy to control.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium-rich manganese-based positive electrode material with high specific capacity, low price, excellent performance, relatively stable structure and high safety, namely the application, and the specific scheme is as follows:
a preparation method of a gradient composite doped lithium-rich manganese-based material comprises the following steps:
(1) preparing doped lithium hydroxy nickelate nanoparticles: the preparation method comprises the following steps of reacting an oxidant and a nickel source solution with lithium hydroxide and doped B metal ions in a reaction kettle under certain conditions to prepare the lithium ion battery; the certain conditions are that the pH value of the solution is between 4.5 and 6.5, the temperature is between 60 and 80 ℃, and a surfactant is added for modification;
(2) preparing the lithium-rich manganese-based material by secondary doping and cladding: doping and coating the concentrated slurry obtained in the step one under a certain condition by adopting a manganese source, a doped A metal ion and a lithium source;
(3) drying and sintering the lithium-rich manganese-based material: drying and sintering the centrifugally separated lithium-rich manganese-based material precursor;
the A metal ions are Mn, Al, Ti, Sn, Nb, Mg or Cr;
the metal ions B are Mn, Al, Ti, Sn, Nb, Mg or Cr;
the chemical formula of the gradient composite doped lithium-rich manganese-based material is as follows: li1-x[LixNix-yByO2x]Mn[(1-x)/2]- zAzO3(1-x)/2Wherein A or B = Mn, Al, Ti, Sn, Nb, Mg or Cr, wherein 0.3. gtoreq.x.gtoreq.0.25, 0.1. gtoreq.y > 0, 0.1. gtoreq.z > 0.
The certain conditions of the step (2) are that the temperature is controlled to be between 60 and 80 ℃, and the PH value is between 6 and 10.
The sintering temperature in the step (3) is 0-900 ℃, and the sintering time is 6-16 hours.
The nickel source in the step (1) is one of nickel acetate or nickel hydroxide.
The lithium source in the step (2) is one of lithium carbonate or lithium hydroxide.
The surfactant in the step (1) is an organic polymer which is easily soluble in water, has a low decomposition temperature and only contains C, H, O trielements.
The gradient composite doped lithium-rich manganese-based material is used as an active substance of the positive electrode of the lithium ion battery.
According to the general formula of the prepared lithium-rich manganese-based material and the volume a liter of the reaction kettle, 0.2a liter of solution with Ni source concentration of (x-y) mol/L, 0.2a liter of solution with Mn source concentration of { [ (1-x)/2] -z } mol/L and 0.1a liter of solution with A source concentration of (2 z) mol/L are firstly prepared.
The method comprises the following specific steps:
(1) 0.5a liter of deionized water is added into the reaction kettle, and then 0.1a (x-y) mol of K is added in sequence2S2O8(oxidizing agent), (0.2 ay) mol of B metal ion (i.e., B in the chemical formula), (0.2ax) mol of LiOH while heating with stirring.
(2) When the temperature of the solution in the reaction kettle rises to 60 ℃, adding a surfactant (0.5-0.6% of the weight of the lithium-rich manganese-based material prepared theoretically), controlling the pH of the solution to be 4.5-6.5, starting to introduce the Ni source solution at a certain speed, and slowly raising the temperature to keep the temperature of the reaction kettle between 60-80 ℃.
(3) After the reaction is finished, centrifugally concentrating to keep the suspension in the reaction kettle at about 0.4a liter; then, 0.005a { [ (1-x)/2] -z } l of hydrogen peroxide was added thereto with stirring.
(4) The temperature of the reaction kettle is about 60 ℃, and a Mn source, A metal ions (namely A in a chemical formula) and a precipitator (prepared from ammonia water, ammonium bicarbonate, ammonium carbonate or sodium hydroxide and the like) prepared in the step are introduced into the reaction kettle in a parallel flow manner and stirred simultaneously. Then Li source (1-x) mol lithium source is added, the temperature of the suspension in the reaction kettle is kept between 60 ℃ and 80 ℃, and the pH value is kept between 6 and 10.
(5) The reaction lasts for 1-3 hours, and after the reaction is finished, centrifugal separation and washing are carried out.
(6) And (3) reprocessing the separated washing liquid, placing the separated solid precursor into a sintering furnace, roasting for 6-16 hours at the temperature of 0-860 ℃, and cooling to obtain the lithium-rich manganese-based anode material. The invention has the following advantages: (1) preparing step by step, gradient coating and composite doping; (2) the preparation of the material is modified by adopting the composite surfactant (the uniformity of mixed materials is improved, and the porosity of the material is increased, so that the activity of the material is improved).
Drawings
Fig. 1 is an XRD pattern of the lithium-rich manganese-based material synthesized in example 1;
FIG. 2 is a 10000 times electron micrograph of the lithium-rich manganese-based material synthesized in example 1;
FIG. 3 is a graph of the cycling performance of the lithium-rich manganese-based material synthesized in example 1 (0.2C charged, 0.2C discharged);
fig. 4 is a first 0.2C discharge plot of the lithium-rich manganese-based material synthesized in example 1.
Detailed Description
Example 1 NiSO was first prepared according to the general formula and using a 10 liter reaction vessel volume 42 liters of solution with the concentration of 0.2mol/L and MnSO 42 liters of 0.325mol/L solution and Al2(SO4)31 liter of a solution having a concentration of 0.05mol/L and 1 liter of a solution of a precipitant (aqueous ammonia 0.75 mol/L). 5 liters of deionized water is added into a reaction kettle, and then 0.2mol of K is added in sequence2S2O80.05mol of Ti2O30.5mol of LiOH, while stirring with heating. When the temperature of the solution in the reaction kettle rises to 60 ℃, 0.55g of PEG2000 is added, and the prepared NiSO is introduced at the beginning of 100ml/min4And slowly raising the temperature of the solution to keep the temperature of the reaction kettle between 60 and 70 ℃. After the reaction is finished, centrifugally concentrating to keep the suspension in the reaction kettle at about 4 liters; then 0.041L of hydrogen peroxide is added and stirred at the same time. The temperature of the reaction kettle is about 60 ℃, and prepared MnSO is introduced into the reaction kettle in a parallel flow manner4、Al2(SO4)3And a precipitant while stirring. Subsequently adding 0.75mol of LiOH; the temperature of the suspension in the reaction kettle is kept between 60 and 70 ℃, and the PH value is kept at about 8.5. The reaction was continued for 3 hours, and after the reaction was completed, the reaction mixture was centrifuged and washed. Retreating the separated washing liquid, putting the separated solid precursor into a sintering furnace, setting the heating rate to be 5 DEG/min, sintering at 450 ℃ for 3 hours and at 820 ℃ for 16 hoursNaturally cooling to obtain the lithium-rich manganese-based positive electrode material Li0.75[Li0.25Ni0.2Ti0.05O0.5]Mn0.325Al0.05O1.125。
XRD and electrical property test are carried out on the material, figure 1 is an XRD spectrum of the lithium-rich manganese-based solid solution material synthesized by the method in the embodiment, the spectrum has a characteristic diffraction peak near a 2 theta angle of 20-25 degrees, and the material is of a layered structure and accords with the structural characteristics of the lithium-rich manganese-based material; FIG. 2 is an electron microscope image of 10000 times of the lithium-rich manganese-based solid solution material synthesized by the method in the embodiment; fig. 3 is a cycle performance diagram (0.2C charge and 0.2C discharge) of the lithium-rich manganese-based material synthesized in example 1 of the present invention, and fig. 4 is a first 0.2C discharge diagram of the lithium-rich manganese-based material synthesized in this example, where the first gram capacity is 204mAh/g, which shows that the lithium-rich manganese-based material synthesized by the method has excellent electrochemical performance.
Example 2
According to the general formula and the volume of the reactor used, 10 liters, NiSO is first prepared42 liters of solution with the concentration of 0.23mol/L and MnSO 42 liters of 0.305mol/L solution, Al2(SO4)31 liter of a solution having a concentration of 0.06mol/L and 1 liter of a solution of a precipitant (aqueous ammonia 0.73 mol/L). 5 liters of deionized water is added into a reaction kettle, and then 0.2mol of K is added in sequence2S2O80.04mol of Ti2O30.54mol of LiOH, while stirring with heating. When the temperature of the reaction kettle solution rises to 60 ℃, 0.45g of PEG20000 is added, and the prepared NiSO is introduced at 100ml/min4And slowly raising the temperature of the solution to keep the temperature of the reaction kettle between 60 and 70 ℃. After the reaction is finished, centrifugally concentrating to keep the suspension in the reaction kettle at about 4 liters; then 0.041L of hydrogen peroxide is added and stirred at the same time. The temperature of the reaction kettle is about 60 ℃, and the prepared MnSO is introduced in a parallel flow manner4、Al2(SO4)3And a precipitant while stirring. Then 0.73mol of LiOH is added; the temperature of the suspension in the reaction kettle is kept between 60 and 70 ℃, and the PH value is kept at about 7.5. The reaction was continued for 3 hours, and after the reaction was completed, the reaction mixture was centrifuged and washed. The separated washing liquid is reprocessed,putting the separated solid precursor into a sintering furnace, setting the heating rate to be 5 DEG/min, sintering for 3 hours at 450 ℃, roasting for 10 hours at 860 ℃, and naturally cooling to obtain the lithium-rich manganese-based anode material Li0.73[Li0.27Ni0.23Ti0.04O0.54]Mn0.305Al0.06O1.1。
Example 3 NiSO was first prepared according to the general formula and a volume of 10 liters using a reaction vessel 42 liters of solution with the concentration of 0.2mol/L and MnSO 42 liters of solution with the concentration of 0.325mol/L and SnSO 41 liter of a solution having a concentration of 0.1mol/L and 1 liter of a solution of a precipitant (aqueous ammonia 0.75 mol/L). 5 liters of deionized water is added into a reaction kettle, and then 0.2mol of K is added in sequence2S2O80.05mol of Ti2O30.5mol of LiOH, while stirring with heating. When the temperature of the solution in the reaction kettle rises to 60 ℃, 0.45g of PVA is added, and the NiSO prepared in the step is introduced at 100ml/min4And slowly raising the temperature of the solution to keep the temperature of the reaction kettle between 60 and 70 ℃. After the reaction is finished, centrifugally concentrating to keep the suspension in the reaction kettle at about 4 liters; then 0.041L of hydrogen peroxide is added and stirred at the same time. Subsequently adding 0.75mol of LiOH; the temperature of the reaction kettle is about 60 ℃, and the prepared MnSO is introduced in a parallel flow manner4、SnSO4And a precipitant while stirring. The temperature of the suspension in the reaction kettle is kept at about 80 ℃, and the pH value is kept at about 9. The reaction was continued for 3 hours, and after the reaction was completed, the reaction mixture was centrifuged and washed. Reprocessing the separated washing liquid, putting the separated solid precursor into a sintering furnace, setting the heating rate to be 5 DEG/min, sintering for 3 hours at 450 ℃, roasting for 15 hours at 850 ℃, and naturally cooling to obtain the lithium-rich manganese-based anode material Li0.75[Li0.25Ni0.2Ti0.05O0.5]Mn0.325Sn0.05O1.125。
Example 4
According to the general formula and the volume of the reactor used, 10 liters, first Ni (NO) was prepared3）22 liters of solution with the concentration of 0.2mol/L and MnSO42L of a 0.325mol/L solution, Mg (Cl)21 liter of solution with the concentration of 0.1mol/L and precipitator(Ammonia 0.75mol/L) in 1 liter. 5 liters of deionized water is added into a reaction kettle, and then 0.2mol of K is added in sequence2S2O80.1mol of Al (Cl)30.5mol of LiOH, while stirring with heating. When the temperature of the solution in the reaction kettle rises to 60 ℃, 0.5g of sucrose is added, and the prepared NiSO is introduced at the beginning of 100ml/min4And slowly raising the temperature of the solution to keep the temperature of the reaction kettle between 60 and 70 ℃. After the reaction is finished, centrifugally concentrating to keep the suspension in the reaction kettle at about 4 liters; then 0.041L of hydrogen peroxide is added and stirred at the same time. The temperature of the reaction kettle is about 60 ℃, and the prepared MnSO is introduced in a parallel flow manner4、Mg(Cl)2And a precipitant while stirring. Subsequently, 0.375mol of Li are added2CO3(ii) a The temperature of the suspension in the reaction kettle is kept at about 80 ℃, and the pH value is kept at about 10. The reaction was continued for 3 hours, and after the reaction was completed, the reaction mixture was centrifuged and washed. Reprocessing the separated washing liquid, putting the separated solid precursor into a sintering furnace, setting the heating rate to be 5 DEG/min, sintering for 3 hours at 450 ℃, roasting for 12 hours at 860 ℃, and naturally cooling to obtain the lithium-rich manganese-based anode material Li0.75[Li0.25Ni0.2Al0.05O0.5]Mn0.325Mg0.05O1.125。
Example 5
According to the general formula and the volume of the reactor used, 10 liters, NiSO is first prepared42 liters of solution with the concentration of 0.2mol/L and MnSO 42 liters of solution with the concentration of 0.85mol/L and Cr2(SO4)31 liter of a solution having a concentration of 0.03mol/L and 1 liter of a solution of a precipitant (ammonium carbonate 0.75 mol/L). 5 liters of deionized water is added into a reaction kettle, and then 0.2mol of K is added in sequence2S2O80.1mol of Al (Cl)30.5mol of LiOH, while stirring with heating. When the temperature of the reaction kettle solution rises to 60 ℃, 0.5g of PEG4000 is added, and the prepared NiSO is introduced at the beginning of 100ml/min4And slowly raising the temperature of the solution to keep the temperature of the reaction kettle between 60 and 70 ℃. After the reaction is finished, centrifugally concentrating to keep the suspension in the reaction kettle at about 4 liters; then 0.041L of hydrogen peroxide is added and stirred at the same time. The temperature of the reaction kettle is about 60 DEG CRight, start co-current introduction of formulated MnSO4、Al(Cl)3And a precipitant while stirring. Subsequently, 0.375mol of Li are added2CO3(ii) a The temperature of the suspension in the reaction kettle is kept at about 80 ℃, and the pH value is kept at about 8. The reaction was continued for 3 hours, and after the reaction was completed, the reaction mixture was centrifuged and washed. Reprocessing the separated washing liquid, putting the separated solid precursor into a sintering furnace, setting the heating rate to be 5 DEG/min, sintering for 3 hours at 450 ℃, roasting for 12 hours at 860 ℃, and naturally cooling to obtain the lithium-rich manganese-based anode material Li0.75[Li0.25Ni0.2Al0.05O0.5]Mn0.345Cr0.03O1.125。
Example 6:
according to the general formula and the volume of the reactor used, 10 liters, NiSO is first prepared42 liters of solution with the concentration of 0.25mol/L and MnSO 42 liters of a solution having a concentration of 0.34mol/L and 1 liter of a solution of a precipitant (aqueous ammonia 0.7 mol/L). 5 liters of deionized water is added into a reaction kettle, and then 0.3mol of K is added in sequence2S2O80.1mol of Ti (SO)4)20.6mol of LiOH, while stirring with heating. When the temperature of the solution in the reaction kettle rises to 60 ℃, 0.4g of PVA is added, and the prepared NiSO is introduced at the beginning of 100ml/min4And slowly raising the temperature of the solution to keep the temperature of the reaction kettle between 60 and 70 ℃. After the reaction is finished, centrifugally concentrating to keep the suspension in the reaction kettle at about 4 liters; then 0.041L of hydrogen peroxide is added and stirred at the same time. The temperature of the reaction kettle is about 60 ℃, and the prepared MnSO is introduced in a parallel flow manner4And a precipitant while stirring. Subsequently, 0.35mol of Li are added2CO3And 0.01mol of Nb2O5(ii) a The temperature of the suspension in the reaction kettle is kept at about 80 ℃, and the pH value is kept at about 8. The reaction was continued for 3 hours, and after the reaction was completed, the reaction mixture was centrifuged and washed. Reprocessing the separated washing liquid, putting the separated solid precursor into a sintering furnace, setting the heating rate to be 5 DEG/min, burning for 3 hours at 450 ℃, roasting for 15 hours at 810 ℃, and naturally cooling to obtain the lithium-rich manganese-based anode material Li0.7[Li0.3Ni0.25Ti0.05O0.6]Mn0.34Nb0.01O1.05。
The above-mentioned embodiments are merely illustrative of the inventive concept and are not intended to limit the scope of the invention, which is defined by the claims and the insubstantial modifications of the inventive concept can be made without departing from the scope of the invention.
Claims (7)
1. A preparation method of a gradient composite doped lithium-rich manganese-based material is characterized by comprising the following steps:
(1) preparing doped lithium hydroxy nickelate nanoparticles: the preparation method comprises the following steps of reacting an oxidant and a nickel source solution with lithium hydroxide and doped B metal ions in a reaction kettle under certain conditions to prepare the lithium ion battery; the certain conditions are that the pH value of the solution is between 4.5 and 6.5, the temperature is between 60 and 80 ℃, and a surfactant is added for modification;
(2) preparing the lithium-rich manganese-based material by secondary doping and cladding: doping and coating the concentrated slurry obtained in the step one under a certain condition by adopting a manganese source, a doped A metal ion and a lithium source;
(3) drying and sintering the lithium-rich manganese-based material: drying and sintering the centrifugally separated lithium-rich manganese-based material precursor;
the A metal ions are Mn, Al, Ti, Sn, Nb, Mg or Cr;
the metal ions B are Mn, Al, Ti, Sn, Nb, Mg or Cr;
the chemical formula of the gradient composite doped lithium-rich manganese-based material is as follows: li1-x[LixNix-yByO2x]Mn[(1-x)/2]- zAzO3(1-x)/2Wherein A or B = Mn, Al, Ti, Sn, Nb, Mg or Cr, wherein 0.3. gtoreq.x.gtoreq.0.25, 0.1. gtoreq.y > 0, 0.1. gtoreq.z > 0.
2. The method for preparing the gradient composite doped lithium-rich manganese-based material according to claim 1, wherein the method comprises the following steps: the certain conditions of the step (2) are that the temperature is controlled to be between 60 and 80 ℃, and the PH value is between 6 and 10.
3. The method for preparing the gradient composite doped lithium-rich manganese-based material according to claim 1, wherein the method comprises the following steps: the sintering temperature in the step (3) is 0-900 ℃, and the sintering time is 6-16 hours.
4. The method for preparing the gradient composite doped lithium-rich manganese-based material according to claim 1, wherein the method comprises the following steps: the nickel source in the step (1) is one of nickel acetate or nickel hydroxide.
5. The method for preparing the gradient composite doped lithium-rich manganese-based material according to claim 1, wherein the method comprises the following steps: the lithium source in the step (2) is one of lithium carbonate or lithium hydroxide.
6. The method for preparing the gradient composite doped lithium-rich manganese-based material according to claim 1, wherein the method comprises the following steps: the surfactant in the step (1) is an organic polymer which is easily soluble in water, has a low decomposition temperature and only contains C, H, O trielements.
7. The gradient composite doped lithium-rich manganese-based material prepared by the preparation method of the gradient composite doped lithium-rich manganese-based material according to claim 1 is used as a positive electrode active material of a lithium electronic battery.
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