CN111661880B - Positive electrode material and preparation method thereof - Google Patents
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 55
- 239000011572 manganese Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 31
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 17
- 229910017052 cobalt Inorganic materials 0.000 claims description 17
- 239000010941 cobalt Substances 0.000 claims description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 241000080590 Niso Species 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 2
- 239000010406 cathode material Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- 230000014759 maintenance of location Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000010405 anode material Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a positive electrode material and a preparation method thereof. The positive electrode material provided by the invention has a structure shown in a formula (1): li x Ni a Co b Mn c O 2 Formula (1); wherein a is more than 0.08 and less than 0.3, b is more than 0.05 and less than 0.15, and c is more than 0.5 and less than 0.6; x is more than 1.1 and less than 1.3. The positive electrode material provided by the invention can effectively improve the specific capacity, the specific energy density and the capacity/energy conservation rate of the battery. The invention also provides a preparation method of the cathode material, and the preparation method is simple and easy to implement and convenient for large-scale production and application.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a positive electrode material and a preparation method thereof.
Background
The change of energy ways changes the life ways of human beings, and the life ways with high carbon emission bring many challenges to the survival of human beings, so that the replacement of traditional energy sources by new energy is imminent. At present, the main mode of new energy is lithium ion batteries, and the increasing living standard of human beings puts higher requirements on the lithium ion batteries, such as higher specific capacity and energy density and better electrochemical stability.
In the high specific capacity lithium-rich cathode material, the mode of improving the electrochemical performance is mainly cladding or doping modification. The surface is coated with a layer of material which is uniformly conductive and can block the electrolyte, and the circulation stability is improved by reducing the side reaction of the electrode material-electrolyte interface. The method also adjusts and controls different sintering modes (changing temperature and fluxing agent) for the same battery material to obtain materials with different stacking fault (defect) concentrations, thereby adjusting and controlling the performance of the anode material.
In the prior art, from the aspect of a synthesis method, the method for improving the capacity and the capacity retention rate mainly comprises the steps of changing the defect concentration by processing a material through high/low temperature or increasing a fluxing agent, or improving the electrochemical performance of the material through complex surface coating or doping modification on the surface of the material. These methods are not only time consuming and energy consuming, but also sometimes cumbersome, and it is difficult to produce materials with good consistency on a large scale when coating or doping modification is performed on the material surface interface.
Disclosure of Invention
In view of the above, the present invention provides a positive electrode material and a method for preparing the same. The positive electrode material provided by the invention can effectively improve the capacity and capacity retention rate of the battery. Meanwhile, the preparation method provided by the invention is simple and feasible, and is convenient for large-scale production and application.
The invention provides a positive electrode material, which has a structure shown in a formula (1):
Li x Ni a Co b Mn c O 2 formula (1);
wherein the content of the first and second substances,
0.08＜a＜0.3，0.05＜b＜0.15，0.5＜c＜0.6；
1.1＜x＜1.3。
preferably, the structure of formula (1) is: li 1.218 Ni 0.101 Co 0.106 Mn 0.565 O 2 。
The invention also provides a preparation method of the anode material in the technical scheme, which comprises the following steps:
a) nickel source compound, cobalt source compound, manganese source compound, Na 2 CO 3 And NH 4 OH is coprecipitated in solvent to generate (Ni) 1/6 Co 1/6 Mn 4/6 )CO 3 A precursor;
b) mixing the precursor with lithium carbonate and ball-milling to obtain a ball grinding material;
c) and sintering the ball milling material to obtain the anode material shown in the formula (1).
Preferably, the nickel source compound is NiSO 4 ·6H 2 O；
The cobalt source compound is CoSO 4 ·7H 2 O；
The manganese source compound is MnSO 4 ·4H 2 O。
Preferably, in the step a), the reaction temperature is 55-65 ℃.
Preferably, the step a) specifically comprises: solution of nickel source compound, solution of cobalt source compound, solution of manganese source compound, and Na 2 CO 3 Solution and NH 4 OH solution is mixed for coprecipitation reaction to generate (Ni) 1/6 Co 1/6 Mn 4/6 )CO 3 A precursor;
the concentration of the nickel source compound solution is 1.9-2.1 mol/L;
the concentration of the cobalt source compound solution is 1.9-2.1 mol/L;
the concentration of the manganese source compound solution is 1.9-2.1 mol/L;
the Na is 2 CO 3 The concentration of the solution is 1.9-2.1 mol/L;
the NH 4 The concentration of the OH solution is 0.15-0.25 mol/L;
the molar ratio of the nickel source compound to the cobalt source compound to the manganese source compound is 1: 0.17-1.88: 1.67-7.5;
the NH 4 The addition amount of OH is such that the pH value of the system is 7.6-7.9.
Preferably, in the step b), the molar ratio of the precursor to the lithium carbonate is 1 to (0.75-1.6);
the rotation speed of the ball milling is 50-200 rpm, and the time is 12-24 h.
Preferably, in the step c), the sintering temperature is 450-850 ℃ and the sintering time is 14-20 hours.
Preferably, in the step c), the sintering specifically includes:
firstly heating to 450-550 ℃, preserving heat for 4-5 h, then heating to 780-850 ℃, and preserving heat for 10-15 h;
the temperature rise rate is 3-5 ℃/min.
Preferably, the step a) further comprises, after the reaction: washing and drying;
the drying is vacuum drying;
the drying temperature is 70-90 ℃.
The invention provides a positive electrode material, which has a structure shown in a formula (1): li x Ni a Co b Mn c O 2 Formula (1); wherein a is more than 0.08 and less than 0.3, b is more than 0.05 and less than 0.15, and c is more than 0.5 and less than 0.6; x is more than 1.1 and less than 1.3. The positive electrode material provided by the invention can effectively improve the specific capacity, the specific energy density and the capacity/energy conservation rate of the battery. The invention also provides a preparation method of the cathode material, and the preparation method is simple and feasible and is convenient for large-scale production and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an XRD pattern of the product obtained in example 1;
FIG. 2 is a TEM image of the product obtained in example 1;
FIG. 3 is a graph showing the specific capacity retention rate in example 2;
FIG. 4 is a graph showing the specific energy retention rate in example 2.
Detailed Description
The invention provides a positive electrode material, which has a structure shown in a formula (1):
Li x Ni a Co b Mn c O 2 formula (1);
wherein the content of the first and second substances,
0.08＜a＜0.3，0.05＜b＜0.15，0.5＜c＜0.6；
1.1＜x＜1.3。
in the present invention, the positive electrode material is preferably Li 1.218 Ni 0.101 Co 0.106 Mn 0.565 O 2 。
The invention also provides a preparation method of the anode material in the technical scheme, which comprises the following steps:
a) nickel source compound, cobalt source compound, manganese source compound, Na 2 CO 3 And NH 4 OH is coprecipitated in solvent to generate (Ni) 1/6 Co 1/6 Mn 4/6 )CO 3 A precursor;
b) mixing the precursor with lithium carbonate and ball-milling to obtain a ball grinding material;
c) and sintering the ball milling material to obtain the anode material shown in the formula (1).
With respect to step a):
the nickel sourceThe compound is preferably NiSO 4 ·6H 2 And O. The cobalt source compound is preferably CoSO 4 ·7H 2 And O. The manganese source compound is preferably MnSO 4 ·4H 2 And O. The solvent is preferably water.
Said step a) preferably comprises in particular: solution of nickel source compound, solution of cobalt source compound, solution of manganese source compound, and Na 2 CO 3 Solution and NH 4 OH solution is mixed for coprecipitation reaction to generate (Ni) 1/6 Co 1/6 Mn 4/6 )CO 3 And (3) precursor.
The concentration of the nickel source compound solution is preferably 1.9-2.1 mol/L, and in some embodiments of the invention, the concentration is 2.0 mol/L. The concentration of the cobalt source compound solution is preferably 1.9-2.1 mol/L, and in some embodiments of the invention, the concentration is 2.0 mol/L. The concentration of the manganese source compound solution is preferably 1.9-2.1 mol/L, and in some embodiments of the invention, the concentration is 2.0 mol/L. The Na is 2 CO 3 The concentration of the solution is preferably 1.9-2.1 mol/L, and in some embodiments of the invention, the concentration is 2.0 mol/L. The NH 4 The concentration of the OH solution is preferably 0.15-0.25 mol/L, and in some embodiments of the invention, the concentration is 0.2 mol/L. The compound solutions are preferably aqueous solutions of the compounds. Wherein, Na 2 CO 3 Is a precipitating agent; NH (NH) 4 OH plays a role in adjusting the pH value and the complexing agent.
Wherein the molar ratio of the nickel source compound to the cobalt source compound to the manganese source compound is 1: 0.17-1.88: 1.67-7.5; in one embodiment of the invention, the molar ratio is 1: 6. The Na is 2 CO 3 The mass ratio of the nickel source compound to the nickel source compound is preferably 1 to (7.9-10.5). The NH 4 The addition amount of OH is preferably selected to ensure that the pH value of the system is 7.6-7.9; in one embodiment of the invention, the pH is controlled to 7.8.
In the invention, when mixing materials, the operation mode is preferably as follows: firstly, mixing a nickel source compound solution, a cobalt source compound solution and a manganese source compound solution, and then adding Na 2 CO 3 Solution and NH 4 The OH solution was slowly added dropwise to the system.
In the invention, when the reaction is carried out after the materials are mixed, the reaction temperature is preferably controlled to be 55-65 ℃; in one embodiment of the invention, the reaction temperature is 60 ℃. After full reaction, (Ni) is generated 1/6 Co 1/6 Mn 4/6 )CO 3 The precursor precipitates.
In the present invention, after the above reaction, the following post-treatments are preferably further performed in this order: carrying out solid-liquid separation to obtain solid powder; the solid powder was washed with distilled water to remove residual Na + (ii) a And then carrying out vacuum drying, wherein the drying temperature is preferably 70-90 ℃, and in some embodiments, the drying is carried out for more than 20 hours at 80 ℃. By the above-mentioned post-treatment, (Ni) is obtained 1/6 Co 1/6 Mn 4/6 )CO 3 And (3) precursor.
With respect to step b):
said (Ni) 1/6 Co 1/6 Mn 4/6 )CO 3 The mol ratio of the precursor to the lithium carbonate is preferably 1 to (0.75-1.6); in one embodiment of the invention, the molar ratio is 1: 0.75. The rotation speed of the ball milling is preferably 50-200 rpm; in one embodiment of the invention, the rotational speed is 60 rpm. The ball milling time is preferably 12-24 h. The ball milling may be performed using a horizontal ball mill. Through the ball milling, the particle size of the primary particles of the obtained ball grinding material is controlled to be 50-120 nm, and the particle size of the secondary particles is controlled to be 15-30 mu m.
With respect to step c):
the sintering temperature is preferably 450-850 ℃, and the heat preservation time is preferably 14-20 h. More preferably, the sintering specifically comprises: the temperature is raised to 450-550 ℃ and kept for 4-5 h, and then raised to 780-850 ℃ and kept for 10-15 h. The heating rate is preferably 3-5 ℃/min; in one embodiment of the invention, the ramp rate is 5 deg.C/min. If the first sintering temperature is too low, the material elements are easily distributed unevenly, so that the material fails, and if the second sintering temperature is too low or too high, the first electrochemical charge-discharge efficiency (discharge capacity/charge capacity) of the material is reduced, the first discharge capacity is reduced, and the cycle retention rate is reduced. If the holding time is too long, the discharge capacity of the material is easily reduced. In one embodiment of the present invention, the sintering regime is: heating to 500 deg.C at 5 deg.C/min, maintaining for 5 hr, heating to 800 deg.C at 5 deg.C/min, maintaining for 12 hr, and furnace cooling. After the sintering treatment, the positive electrode material shown in the formula (1) is obtained. Through the above preparation, the finally obtained material represented by formula (1) is layered in crystal structure, as shown in fig. 2. The material can effectively improve the electrochemical performance of the battery.
The preparation method provided by the invention is simple and feasible, the new material is obtained in a multi-component regulation mode, the uniformity is better, the overall performance is more stable, and the material with good consistency can be easily obtained in mass production.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
1.1 preparation
Mixing NiSO 4 ·6H 2 Aqueous solution of O (2.0mol/L), CoSO 4 ·7H 2 Aqueous solution of O (2.0mol/L), MnSO 4 ·4H 2 An aqueous solution of O (2.0mol/L) was continuously pumped into a stirred tank reactor (capacity 50L) in a volume ratio of 1: 6. At the same time, adding Na 2 CO 3 Solution (2.0mol/L) and NH 4 OH solution (0.2mol/L) was added dropwise to the reactor, in which Na was added 2 CO 3 With NiSO 4 ·6H 2 The molar ratio of O is 1: 1, NH 4 OH to make the pH value of the system be 7.8, and making coprecipitation reaction for 80 hr at 60 deg.C to form (Ni) 1/ 6 Co 1/6 Mn 4/6 )CO 3 And (4) precipitating.
The formed precipitate was washed several times with distilled water to remove residual Na + Drying at 80 deg.C for more than 20 hr in vacuum box to obtain (Ni) 1/6 Co 1/6 Mn 4/6 )CO 3 And (3) precursor.
Mixing the precursor with Li 2 CO 3 Mixing according to the molar ratio of 1: 0.75, ball milling for 12h on a horizontal ball mill at the rotating speed of 60rpm, and then placing the mixture in a compression machineAnd (3) heating to 500 ℃ at the speed of 5 ℃/min in an air oven, keeping the temperature for 5h, continuing heating to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 12h, and cooling along with the oven to obtain the product.
1.2 characterization
(1) The product obtained was subjected to ICP-OES testing and showed the composition: li 1.218 Ni 0.101 Co 0.106 Mn 0.565 O 2 。
(2) The x-ray diffraction test of the obtained product shows that the result is shown in figure 1, and figure 1 is the XRD pattern of the product obtained in example 1. The results show that the obtained material belongs to the R-3m space group structure.
(3) The transmission electrolysis test was carried out on the obtained product, and the result is shown in FIG. 2, FIG. 2 is a TEM image of the product obtained in example 1. The results show that the obtained material is a layered material with a layered crystal structure.
Example 2
Assembling a CR2032 button cell:
80% of the positive electrode material active substance obtained in the example 1, 10% of acetylene black and 10% of polyvinylidene fluoride adhesive are mixed, then the obtained slurry is coated on an aluminum foil, and the aluminum foil is dried in an oven at 80 ℃ for more than 8 hours to obtain a positive electrode piece. And punching the obtained positive pole piece into a wafer with the diameter of 13mm on a punching machine, compacting the wafer under the pressure of 8MPa, and drying the wafer in a vacuum tube at the temperature of 80 ℃. The pole pieces were then transferred to an argon glove box (H) 2 O<0.1p.p.m，O 2 <0.1p.p.m), a lithium metal sheet is used as a negative electrode, Celgard 2502 is used as a diaphragm, and LiPF is used for assembling the battery 6 The solution is electrolyte (concentration is 1M; solvent is mixed solution of ethylene carbonate EC and dimethyl carbonate DMC in volume ratio of 3: 7). And assembling to obtain the CR2032 button battery.
The electrochemical performance of the assembled battery is tested, and the constant-current charging and discharging process is carried out on a blue battery testing system (LAND-CT 2001A). At 0.1C (1C-250 mAh g -1 ) The specific capacity retention rate of 50 cycles of the cycle is tested under the condition, the result is shown in figure 3, figure 3 is a specific capacity retention rate test chart in the embodiment 2, and it can be seen that the specific capacity of the battery reaches 270mAh g -1 Above, circulate for 50 timesAnd the specific capacity retention rate of the battery reaches 99%, and the battery has higher specific capacity and specific capacity retention rate.
The specific energy retention rate of 50 cycles of the cycle is tested under the condition of 0.1C (1C is 250mAh g-1), the result is shown in figure 4, figure 4 is a specific energy retention rate test chart in example 2, and it can be seen that after 50 cycles of the cycle, the specific energy retention rate of the battery reaches 95%, and the specific energy density still reaches 850Wh & Kg & lt- & gt -1 Has higher specific energy density and specific energy retention rate.
From the above test results, it can be seen that the material provided by the present invention has high specific capacity, specific energy density and capacity/energy retention.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A positive electrode material characterized by having a structure represented by formula (1):
Li 1.218 Ni 0.101 Co 0.106 Mn 0.565 O 2 formula (1);
the positive electrode material is prepared by the following preparation method:
a) solution of nickel source compound, solution of cobalt source compound, solution of manganese source compound, and Na 2 CO 3 Solution and NH 4 OH solution is mixed for coprecipitation reaction to generate (Ni) 1/6 Co 1/6 Mn 4/6 )CO 3 A precursor;
the concentration of the nickel source compound solution is 1.9-2.1 mol/L;
the concentration of the cobalt source compound solution is 1.9-2.1 mol/L;
the concentration of the manganese source compound solution is 1.9-2.1 mol/L;
the Na is 2 CO 3 The concentration of the solution is 1.9-2.1 mol/L;
the NH 4 The concentration of the OH solution is 0.15-0.25 mol/L;
the reaction temperature is 55-65 ℃;
b) mixing the precursor with lithium carbonate and ball-milling to obtain a ball grinding material;
the rotation speed of the ball mill is 50-200 rpm, and the time is 12-24 hours;
c) sintering the ball milling material to obtain a positive electrode material shown in a formula (1);
the sintering specifically comprises:
firstly heating to 450-550 ℃, preserving heat for 4-5 h, then heating to 780-850 ℃, and preserving heat for 10-15 h;
the temperature rising rate is 3-5 ℃/min.
2. A method for producing the positive electrode material according to claim 1, comprising the steps of:
a) solution of nickel source compound, solution of cobalt source compound, solution of manganese source compound, and Na 2 CO 3 Solution and NH 4 OH solution is mixed for coprecipitation reaction to generate (Ni) 1/6 Co 1/6 Mn 4/6 )CO 3 A precursor;
the concentration of the nickel source compound solution is 1.9-2.1 mol/L;
the concentration of the cobalt source compound solution is 1.9-2.1 mol/L;
the concentration of the manganese source compound solution is 1.9-2.1 mol/L;
the Na is 2 CO 3 The concentration of the solution is 1.9-2.1 mol/L;
the NH 4 The concentration of the OH solution is 0.15-0.25 mol/L;
the reaction temperature is 55-65 ℃;
b) mixing the precursor with lithium carbonate and ball-milling to obtain a ball grinding material;
the rotation speed of the ball mill is 50-200 rpm, and the time is 12-24 hours;
c) sintering the ball milling material to obtain a positive electrode material shown in a formula (1);
the sintering specifically comprises:
firstly heating to 450-550 ℃, preserving heat for 4-5 h, and then heating to 780-850 ℃, preserving heat for 10-15 h;
the temperature rising rate is 3-5 ℃/min.
3. The method according to claim 2, wherein the nickel source compound is NiSO 4 ·6H 2 O；
The cobalt source compound is CoSO 4 ·7H 2 O；
The manganese source compound is MnSO 4 ·4H 2 O。
4. The preparation method according to claim 2, wherein the molar ratio of the nickel source compound to the cobalt source compound to the manganese source compound is 1: 0.17 to 1.88: 1.67 to 7.5;
the NH 4 The addition amount of OH is such that the pH value of the system is 7.6-7.9.
5. The preparation method according to claim 2, wherein in the step b), the molar ratio of the precursor to the lithium carbonate is 1 to (0.75-1.6).
6. The method according to claim 2, wherein the step a) further comprises, after the reaction: washing and drying;
the drying is vacuum drying;
the drying temperature is 70-90 ℃.
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