CN117247056A - Preparation and application of cobalt-free positive electrode material of lithium ion battery - Google Patents
Preparation and application of cobalt-free positive electrode material of lithium ion battery Download PDFInfo
- Publication number
- CN117247056A CN117247056A CN202311305404.7A CN202311305404A CN117247056A CN 117247056 A CN117247056 A CN 117247056A CN 202311305404 A CN202311305404 A CN 202311305404A CN 117247056 A CN117247056 A CN 117247056A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- lithium ion
- ion battery
- positive electrode
- free
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 150000004706 metal oxides Chemical class 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 8
- 239000010406 cathode material Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- LIJBHSNTSZDMFV-UHFFFAOYSA-L [OH-].[OH-].[Mn].[Ni++] Chemical compound [OH-].[OH-].[Mn].[Ni++] LIJBHSNTSZDMFV-UHFFFAOYSA-L 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 230000005389 magnetism Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 10
- 208000028659 discharge Diseases 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004761 HSV 900 Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of cobalt-free positive electrode materials of lithium ion batteries, in particular to the field of IPC C01G53, and more particularly relates to preparation and application of a cobalt-free positive electrode material of a lithium ion battery. Including precursor modification, primary roasting and secondary roasting. The cobalt-free anode material coated with the aluminum is prepared by doping and coating the titanium-aluminum bimetallic element, has simple process, excellent cycle performance and higher specific capacity, and fundamentally solves the defect of poor rate performance. Through half battery assembly test, under the conditions of 4.35-2.8V voltage and 0.1CC/0.1CD, the gram capacity of the first discharge can reach more than 199.8mAh/g, and after 50 weeks circulation at normal temperature, the capacity retention rate can reach more than 90%, so that the battery has a wide market application prospect when applied to the field of power batteries.
Description
Technical Field
The invention relates to the technical field of cobalt-free positive electrode materials of lithium ion batteries, in particular to the field of IPC C01G53, and more particularly relates to preparation and application of a cobalt-free positive electrode material of a lithium ion battery.
Background
The new energy automobile is taken as an important choice for future transportation and has great market potential and development prospect. Along with the continuous innovation of technology and the positive promotion of policies, new energy automobiles gradually become the first choice of people going out, wherein cobalt is taken as an important raw material of battery materials, cobalt price is in a continuous growth stage, so that ternary battery cells have high cost, cobalt-free materials have certain cost advantages, and high energy density and power density are one of the advantages of cobalt-free single crystal materials, and are widely paid attention in the industry. However, the cobalt-free material has poor surface chemical stability and structural stability, so that the cycle performance and the thermal stability of the cobalt-free material are poor.
CN111916697a discloses a cobalt-free cathode material, a preparation method thereof, a lithium ion battery cathode and a lithium battery. The positive electrode material comprises a core and a shell coating the core, wherein the core is a cobalt-free positive electrode material, and the chemical formula of the core is LiNi x Mn y O 2 Wherein x is more than or equal to 0.55 and less than or equal to 0.95, y is more than or equal to 0.05 and less than or equal to 0.45, and the shell is made of a coating agent and carbon. The method can improve the dispersibility in the coating process of the cobalt-free positive electrode material and improve the conductivity of the cobalt-free positive electrode material. But the workerThe process has complex production process, low gram capacity and low energy density, and limits the application of the process in the field of power batteries.
CN112786827a provides a cobalt-free positive electrode material and a preparation method thereof, the cobalt-free positive electrode material comprises a core and a shell coating the core, the core is doped cobalt-free positive electrode particles, and the shell comprises a doping agent; carrying out infrared spectrum analysis on the cobalt-free positive electrode material, wherein the infrared spectrum analysis is carried out at 520-620 cm -1 The peak area of the peak formed at the position is marked as X and is 800-900 cm -1 The peak area of the formed peak is recorded as Y, and Y/X is more than or equal to 0.010 and less than or equal to 0.035. The interfacial stability of the material is improved by optimizing doping to reduce inter-crystal microcracks and cladding, and meanwhile, residual alkaline substances on the surface are reduced, so that the generation of gas is effectively inhibited, and the failure risk of the battery is further reduced, but the gram capacity is not obviously improved.
Disclosure of Invention
The invention provides a preparation method of a cobalt-free positive electrode material of a lithium ion battery, which comprises the following steps:
step 1: the nickel and manganese soluble salt and the mixed solution of ammonia water and sodium hydroxide are subjected to coprecipitation reaction to prepare a manganese nickel hydroxide binary precursor, and the molecular formula of the manganese nickel hydroxide binary precursor is Ni x Mn y (OH) 2 ；
Step 2: mixing a lithium source, a transition metal oxide and a nickel-manganese binary precursor by a high-speed mixer to obtain a primary mixture;
step 3: placing the primary mixture into an atmosphere roller kiln, and roasting, crushing and screening the primary mixture to obtain a primary roasting material;
step 4: premixing metal oxide, adding the primary roasting material for mixing, mixing by a high-speed mixer, entering a kiln by an atmosphere roller way, carrying out secondary roasting, and sieving to remove magnetism.
The x and y are mole numbers, and the ratio of x to y is (0.6-0.8): (0.2-0.4).
Preferably, the ratio of x to y is (0.7-0.75): (0.2-0.25).
The mixing conditions in the step 2 are as follows: mixing at 500-800 r/min for 30-40 min.
Preferably, the mixing conditions in the step 2 are as follows: mixing at 800r/min for 30min.
The metal element in the transition metal oxide includes one or more of Al, zr, B, mg, sr, la, Y, ce.
Preferably, the metal element in the transition metal oxide includes one or more of Zr and Sr.
Preferably, the transition metal oxide includes SrO and ZrO 2 Strontium can be doped into the interior of the crystal lattice, and a stable coating layer is formed by the low-temperature zirconium coating and the surface of the material, so that the rapid cycle attenuation caused by crystal cracking can be restrained.
The SrO and ZrO 2 The weight ratio is 1: (0.5-2).
The transition metal oxide accounts for 0.1-1.0% of the mass of the primary mixture.
Preferably, the transition metal oxide accounts for 0.2-0.3% of the mass of the primary mixture.
The molar ratio of the nickel-manganese hydroxide to lithium ions in the lithium source is 1: (1.02-1.15).
Preferably, the molar ratio of the nickel manganese hydroxide to lithium ions in the lithium source is 1: (1.05-1.1).
The metal oxide includes at least one of an oxide of titanium and an oxide of aluminum.
The applicant researches find that the transition metal oxide accounts for 0.2-0.3% of the mass of the primary mixture, can stabilize a cobalt-free layered structure, reduce the high-temperature gas production phenomenon, and is possibly that the transition metal compound is doped to be beneficial to metal ions entering into the lattice of the material or coating the surface of the material, so that the material unit cells are orderly stacked and fused, and the lattice defects are reduced, thereby improving the structural stability. Further research shows that the specific proportion of the titanium oxide and the aluminum oxide is doped, so that the cycle performance can be improved, the multiplying power performance can be improved, and the aluminum-titanium double doping can effectively inhibit the volume expansion of the material, inhibit the generation of crystal microcracks and stabilize the three-dimensional structure of the material. Meanwhile, the primary discharge gram capacity can reach more than 199.8mAh/g under the conditions of 4.35-2.8V voltage and 0.1C/0.1C charge-discharge multiplying power by matching with specific secondary sintering temperature and time, and after 50 weeks circulation under normal temperature, the capacity retention rate can reach more than 90 percent, so that the method can be applied to the field of power batteries.
The metal oxide comprises titanium oxide and aluminum oxide, and the weight ratio of the titanium oxide to the aluminum oxide is 1: (0.5-2), aluminum-titanium double doping can better inhibit generation of microcracks of monocrystalline particles, stabilize material structure, improve cycle performance and improve rate performance.
The weight ratio of the titanium oxide to the aluminum oxide is 1: (0.5-2).
Preferably, the weight ratio of the titanium oxide to the aluminum oxide is 1:1.
preferably, the oxide of titanium comprises TiO, tiO 2 And Ti is 2 O 3 One of them.
Preferably, the aluminum oxide comprises Al 2 O 3 And Al (OH) 3 。
The addition amount of the metal oxide accounts for 0.05 to 0.5 percent of the mass of the primary roasting material.
Preferably, the addition amount of the metal oxide accounts for 0.13-0.4% of the mass of the primary roasting material.
The temperature rising rate of the roasting is 1-5 ℃/min.
Preferably, the temperature rising rate of the roasting is 2-4 ℃/min.
Preferably, the temperature rising rate of the roasting is 3 ℃/min.
The D50 particle size of the primary roasting material is 4-6 mu m.
The temperature of the primary roasting is 800-1100 ℃ and the time is 6-12 h.
Preferably, the temperature of the primary roasting is 900 ℃ and the time is 10 hours.
The temperature of the secondary roasting is 600-800 ℃ and the time is 4-8 h.
Preferably, the temperature of the secondary roasting is 800 ℃ and the time is 6 hours.
The second aspect of the invention provides an application of the cobalt-free positive electrode material of the lithium ion battery to preparation of the cobalt-free positive electrode material, and the application of the cobalt-free positive electrode material of the lithium ion battery to an automobile power battery.
Advantageous effects
1. The transition metal oxide accounts for 0.2-0.3% of the mass of the primary mixture, and the transition metal oxide can stabilize the cobalt-free layered structure and reduce the high-temperature gas production phenomenon by matching with the primary roasting parameter.
2. By doping the titanium oxide and the aluminum oxide in a specific ratio, volume expansion during circulation is suppressed, and at the same time, circulation performance is improved.
3. The temperature of the secondary roasting is 600-800 ℃, the time is 4-8 h, and the gram capacity of the primary discharge can reach more than 199.8mAh/g under the conditions of 4.35-2.8V voltage and 0.1C/0.1C charging/discharging multiplying power.
4. The preparation process is simple and convenient, and after 50 weeks of circulation at normal temperature, the capacity retention rate can reach more than 90%, and the use requirement of the power battery field can be met.
Drawings
Fig. 1 is an electron microscope (SEM) image of the positive electrode material of example 1.
Fig. 2 is an electron microscope (SEM) image of the positive electrode material of example 2.
FIG. 3 is an electron microscope (SEM) image of the positive electrode materials of comparative examples 1 to 4.
Fig. 4 is a gram capacity curve for the first discharge of examples 1 and 2.
Fig. 5 is a graph of the gram capacity for first discharge for comparative examples 1-4.
FIG. 6 is a 50-week cycle capacity change curve of examples 1 and 2, wherein the left graph shows a normal temperature (25 ℃) environment test and the right graph shows a high temperature (45 ℃) environment test.
FIG. 7 is a 50-week cycle capacity change curve of comparative examples 1 to 4, in which the left graph is a normal temperature (25 ℃) environment test and the right graph is a high temperature (45 ℃) environment test.
Detailed Description
Example 1
The preparation of the cobalt-free cathode material of the lithium ion battery comprises the following steps:
step 1: mixing solution of soluble salt of nickel and manganese with ammonia water and sodium hydroxidePerforming coprecipitation reaction to prepare nickel manganese hydroxide binary precursor with molecular formula of Ni 75 Mn 25 (OH) 2 ；
Step 2: mixing a lithium source, a transition metal oxide and a nickel-manganese binary precursor by a high-speed mixer to obtain a primary mixture;
step 3: placing the primary mixture into an atmosphere roller kiln, and roasting, crushing and screening the primary mixture to obtain a primary roasting material;
step 4: firstly premixing metal oxide, ensuring uniform mixing, adding a primary roasting material, mixing by a high-speed mixer, entering a kiln by an atmosphere roller way, carrying out secondary roasting, sieving and demagnetizing to obtain the composite material.
The transition metal oxide accounts for 0.3 percent of the mass of the primary mixture, and is SrO and ZrO 2 The SrO and ZrO 2 The weight ratio is 1:0.8.
the molar ratio of the nickel-manganese hydroxide to lithium ions in the lithium source is 1:1.1.
the mixing conditions in the step 2 are as follows: mixing at 800r/min for 30min.
The D50 particle size of the primary calcined material was 4.25. Mu.m.
The temperature of the primary roasting is 900 ℃ and the time is 10 hours.
The temperature of the secondary roasting is 800 ℃ and the time is 6 hours.
The temperature rising rate of the roasting is 3 ℃/min.
The metal oxide is titanium oxide and aluminum oxide, and the weight ratio of the titanium oxide to the aluminum oxide is 1:1, the addition amount of the metal oxide accounts for 0.4% of the mass of the primary roasting material.
The oxide of titanium is TiO 2 The oxide of aluminum is Al (OH) 3 。
Example 2
The detailed description is the same as example 1; except that in example 2: manganese nickel hydroxide binary precursor with molecular formula of Ni 70 Mn 30 (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the The transition metalThe oxide accounts for 0.2% of the mass of the primary mixture; the molar ratio of the nickel-manganese hydroxide to lithium ions in the lithium source is 1:1.05; the addition amount of the metal oxide accounts for 0.3% of the mass of the primary roasting material.
Comparative example 1
The detailed description is the same as example 1; except that in comparative example 1: the metal oxide is titanium oxide, and the titanium oxide is TiO 2 。
Comparative example 2
The detailed description is the same as example 1; except that in comparative example 2: the metal oxide is an oxide of aluminum, and the oxide of aluminum is Al (OH) 3 。
Comparative example 3
The detailed description is the same as example 1; except that in comparative example 3: the weight ratio of the titanium oxide to the aluminum oxide is 1:0.3.
comparative example 4
The detailed description is the same as example 1; except that in comparative example 4: the temperature of the secondary roasting is 400 ℃.
Performance test method
The positive electrode materials in examples and comparative examples were subjected to battery assembly: 9.5g of positive electrode material is weighed, 0.3g of acetylene black (SP) is added as a conductive agent and 0.2g of PVDF (HSV-900) is added as a binder, after full mixing, N-methyl-pyrrolidone (NMP) solvent is added until the solid content is 70 percent for dispersion, after uniform homogenization, aluminum foil with the thickness of 16 mu m is pulled up to prepare a positive electrode plate, a metal lithium plate is used as a negative electrode in an anaerobic glove box, a ceramic diaphragm with the diaphragm of 12+4 mu m is used, and 1mol/L LiPF is used as electrolyte 6 The battery case adopts a (CR 2032) button battery by adopting a standard half-battery configuration, and the battery case is assembled into a half-battery for later battery testing.
1. The cells were tested for gram capacity for initial discharge (mAh/g) at 0.1CC/0.1CD charge/discharge rates in the voltage range of 4.35-2.8V as shown in FIGS. 4 and 5.
2. The capacity retention after 50 weeks of circulation at normal temperature (25 ℃) and high temperature (45 ℃) was measured in examples, respectively, as shown in FIG. 6.
3. The capacity retention after 50 weeks of circulation at normal temperature (25 ℃) and high temperature (45 ℃) of the comparative example was measured, respectively, as shown in FIG. 7.
4. The morphology of the positive electrode material is shown in figures 1-3.
The test data are listed in table 1.
Performance test data
TABLE 1
| Gram capacity (mAh/g) | 50 week Capacity retention (25 ℃ C.) | 50 week Capacity retention (45 ℃ C.) | |
| Example 1 | 199.8 | 90.2 | 82.3 |
| Example 2 | 194.3 | 89.6 | 80.6 |
| Comparative example 1 | 194.7 | 89.5 | 80.8 |
| Comparative example 2 | 195.3 | 89.2 | 80.5 |
| Comparative example 3 | 195.2 | 87.7 | 80.1 |
| Comparative example 4 | 197.5 | 88.7 | 81.1 |
Claims (10)
1. The preparation of the cobalt-free cathode material of the lithium ion battery is characterized by comprising the following steps:
step 1: the nickel and manganese soluble salt and the mixed solution of ammonia water and sodium hydroxide are subjected to coprecipitation reaction to prepare a manganese nickel hydroxide binary precursor, and the molecular formula of the manganese nickel hydroxide binary precursor is Ni x Mn y (OH) 2 ；
Step 2: mixing a lithium source, a transition metal oxide and a nickel-manganese binary precursor by a high-speed mixer to obtain a primary mixture;
step 3: placing the primary mixture into an atmosphere roller kiln, and roasting, crushing and screening the primary mixture to obtain a primary roasting material;
step 4: premixing metal oxide, adding the primary roasting material for mixing, mixing by a high-speed mixer, entering a kiln by an atmosphere roller way, carrying out secondary roasting, and sieving to remove magnetism.
2. The method for preparing the cobalt-free positive electrode material of the lithium ion battery according to claim 1, wherein x and y are molar numbers, and the ratio of x to y is (0.6-0.8): (0.2-0.4).
3. The method for preparing the cobalt-free cathode material of the lithium ion battery according to claim 2, wherein the mixing conditions in the step 2 are as follows: stirring at 500-800 r/min for 30-40 min.
4. A preparation of a cobalt-free positive electrode material for a lithium ion battery according to claim 3, wherein the metal element in the transition metal oxide comprises one or more of Al, zr, B, mg, sr, la, Y, ce.
5. The method for preparing a cobalt-free cathode material for a lithium ion battery according to claim 4, wherein the transition metal oxide accounts for 0.1-1.0% of the mass of the primary mixture.
6. The method for preparing the cobalt-free cathode material of the lithium ion battery according to claim 5, wherein the molar ratio of the manganese nickel hydroxide binary precursor to lithium ions in the lithium source is 1: (1.02-1.15).
7. The method of claim 6, wherein the metal oxide comprises at least one of an oxide of titanium and an oxide of aluminum.
8. The method for preparing the cobalt-free positive electrode material of the lithium ion battery according to claim 1 or 7, wherein the temperature rising rate of the roasting is 1-5 ℃/min.
9. The method for preparing the cobalt-free cathode material of the lithium ion battery according to claim 8, wherein the D50 particle size of the primary roasting material is 4-6 μm.
10. Use of the cobalt-free positive electrode material of a lithium ion battery according to any of claims 1-9 for the preparation of a power battery for automobiles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311305404.7A CN117247056A (en) | 2023-10-10 | 2023-10-10 | Preparation and application of cobalt-free positive electrode material of lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311305404.7A CN117247056A (en) | 2023-10-10 | 2023-10-10 | Preparation and application of cobalt-free positive electrode material of lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117247056A true CN117247056A (en) | 2023-12-19 |
Family
ID=89127667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311305404.7A Pending CN117247056A (en) | 2023-10-10 | 2023-10-10 | Preparation and application of cobalt-free positive electrode material of lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117247056A (en) |
-
2023
- 2023-10-10 CN CN202311305404.7A patent/CN117247056A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20240055577A1 (en) | Cobalt-free positive electrode material, preparation method thereof and lithium ion battery | |
| CN110993903B (en) | Tantalum modified high-nickel cathode material and preparation method and application thereof | |
| CN111446444B (en) | Lithium-rich manganese-based material and preparation method and application thereof | |
| CN112614974A (en) | Preparation method of lithium-containing compound-coated ion-doped ternary positive electrode material | |
| CN110649230B (en) | Nanometer rivet core-shell structure anode material and preparation method thereof | |
| CN114556635A (en) | Positive electrode active material for lithium secondary battery, method for preparing same, and lithium secondary battery comprising same | |
| CN112701276A (en) | Quaternary polycrystalline positive electrode material and preparation method and application thereof | |
| CN113582253B (en) | Quaternary positive electrode material, and preparation method and application thereof | |
| CN112614988B (en) | Positive electrode material and preparation method and application thereof | |
| CN111509219B (en) | Lithium manganate battery material and preparation method thereof | |
| CN110931733B (en) | Surface manganese doping and Li-Mn-PO4Coated high-nickel positive electrode material and preparation method and application thereof | |
| CN111755692A (en) | High-nickel anode material with reconstructed primary particle surface layer and preparation method thereof | |
| CN116805680A (en) | Composite positive electrode material and preparation method and application thereof | |
| CN114105220B (en) | Modified spinel type positive electrode material, preparation method thereof and lithium ion battery positive electrode sheet | |
| CN114561686B (en) | Method for improving compaction density of cobalt-free positive electrode material, cobalt-free positive electrode material and lithium ion battery | |
| CN107516729B (en) | Transition metal layer lithium-containing layered electrode material for symmetrical secondary battery and preparation method and application thereof | |
| CN114927777A (en) | Ultrahigh lithium content material and self-supplementing lithium composite positive electrode material | |
| CN114824267A (en) | Layered lithium nickel manganese oxide positive electrode material and preparation method and application thereof | |
| CN117247056A (en) | Preparation and application of cobalt-free positive electrode material of lithium ion battery | |
| CN111653765A (en) | Preparation method of niobium-doped nickel-cobalt lithium aluminate anode material | |
| CN111634961A (en) | Positive electrode material for lithium ion battery and preparation method thereof | |
| CN111933929B (en) | F-doped anode material and preparation method thereof | |
| CN115663165B (en) | Positive active material and preparation method thereof, positive pole piece and lithium battery | |
| WO2023115289A1 (en) | Nickel-rich material and preparation method therefor, positive electrode plate, battery and electric equipment | |
| WO2021243928A1 (en) | Positive electrode material used for lithium ion battery, preparation method therefor, and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |