CN113410457A - Modification method of lithium-rich oxide positive electrode material - Google Patents
Modification method of lithium-rich oxide positive electrode material Download PDFInfo
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- CN113410457A CN113410457A CN202010187120.2A CN202010187120A CN113410457A CN 113410457 A CN113410457 A CN 113410457A CN 202010187120 A CN202010187120 A CN 202010187120A CN 113410457 A CN113410457 A CN 113410457A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 64
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 26
- 238000002715 modification method Methods 0.000 title abstract description 6
- 239000011572 manganese Substances 0.000 claims abstract description 66
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 54
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010406 cathode material Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 25
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910052786 argon Inorganic materials 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims description 43
- 239000002184 metal Substances 0.000 claims description 43
- 150000003839 salts Chemical class 0.000 claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- 229910021645 metal ion Inorganic materials 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- 239000010453 quartz Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 239000000463 material Substances 0.000 description 25
- 239000010405 anode material Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/48—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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a modification method of a lithium-rich oxide cathode material, belonging to the technical field of new energy. The treatment is carried out by a method of heating and introducing argon, and specifically comprises the following three steps: preparing a carbonate precursor, preparing a lithium-rich manganese-based positive electrode material, and preparing oxygen vacancies generated by heating the lithium-rich manganese-based layered positive electrode material with argon. The method can improve the rate capability and the cycle stability of the lithium-rich manganese-based layered positive electrode material, can inhibit the precipitation of transition metal ions and voltage attenuation in the lithium-rich manganese-based layered positive electrode material, and can reduce the precipitation of oxygen. The method has the advantages of simple synthesis process and high production efficiency, and is suitable for large-scale production. The method has the advantages of easily obtained raw materials required by reactants, no toxicity, low cost, no need of special protection in the production process, easily controlled reaction conditions, high yield of obtained products, good result repeatability and the like.
Description
Technical Field
The invention relates to the technical field of new energy, in particular to a method for modifying a lithium-rich oxide positive electrode material.
Background
The lithium-rich manganese-based layered cathode material has high specific capacity (>250mAh g-1) And high energy density (>1000wh kg-1) The positive electrode of the next generation of high specific energy power battery has received much attention in recent years. Until now, no fully mature lithium-rich manganese-based positive electrode material exists in the global market, mainly because of the problems of poor cycling stability and inability to meet stable capacity and power output in a long cycling state. Secondly, the voltage attenuation is serious in the circulation process, and the power density of the power battery in the use process is seriously reduced due to the voltage attenuation. Also, the low rate capability severely limits the realization of fast charging of the power battery. For these major problems, many fundamental mechanistic studies are currently being conductedMost of these problems are considered to be mainly related to the following points: firstly, the rich lithium battery is accompanied with the generation of oxygen in the process of high-voltage charge and discharge, and the oxygen can react with the electrolyte to accelerate the corrosion of the material and destroy the crystal structure of the material. Secondly, irreversible phase change is accompanied in the charging and discharging process, which causes irreversible change of the crystal structure, such as reduction of interlayer spacing and huge change of crystal stress to collapse the crystal structure. Finally, the transition metal ions react with the electrolyte in the circulating process and are reduced to be dissolved into the electrolyte to cause the damage of the crystal structure. Based on these related studies, many improved methods have been proposed to improve the related properties of lithium-rich manganese-based positive electrode materials, with the most studies being surface coating and bulk or surface metal element doping. These methods all improve the relevant properties of lithium rich materials to some extent. However, these methods are complicated, consume much energy, and have not significant economic benefits. Further improvements are needed on this basis. The surface defect engineering has very important development value, and can change the energy band structure, the electronic structure and the like of the material, which is proved in the catalytic material. Therefore, the introduction of surface defect engineering into the lithium-rich manganese-based cathode material is particularly important. This is mainly because the surface defects can suppress the precipitation of oxygen to some extent, stabilize the crystal structure and increase the interlayer spacing, thus improving the electrochemical performance of the battery. However, the research on the surface defects of the lithium-rich manganese-based cathode material is relatively few, and most preparation processes are relatively complex, so that the practical application is more challenging. Therefore, it is of great importance to develop a more efficient, inexpensive and simple to operate modification process. The lithium-rich cathode material is heated in an argon atmosphere, so that oxygen vacancies can be generated on the surface of the material. The dispensing operation is simple, and the relevant performance of the material can be greatly improved.
Disclosure of Invention
The invention aims to: in order to solve the problems in the background art, a modification method of a lithium-rich oxide cathode material is provided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a modification method of a lithium-rich oxide cathode material adopts a direct heating argon method to generate oxygen vacancies, and comprises the following steps:
s1, preparation of a carbonate precursor:
1) dissolving cobalt metal salt, nickel metal salt and manganese metal salt in pure water to obtain a metal ion mixed solution;
2) preparing a carbonate precipitant solution with the molar concentration of 1-3 mol/L, and adding the precipitant solution into the metal ion mixed solution under magnetic stirring to generate a coprecipitation product;
3) stirring the coprecipitation product for 6-18 hours, then carrying out centrifugal separation on the coprecipitation product, and respectively washing the precipitate with deionized water for three times and absolute ethyl alcohol for two times;
4) and (3) drying the precipitate in an oven at 80 ℃ for 24 hours to obtain a carbonate precursor, wherein the molecular formula of the carbonate precursor is as follows: (Mn)0.1～0.9Ni0.1～0.8Co0～0.5)1.25CO3·2H2O；
S2, preparing a lithium-rich manganese-based layered positive electrode material:
the carbonate precursor obtained in S1 was reacted with LiOH. H2O or Li2CO3Mixing according to the molar ratio of 1 (1-2), and fully grinding to ensure that the particle diameter is 0.5-5 um; uniformly mixing, placing in a muffle furnace, calcining at 700-1000 ℃ for 6-24 hours at a heating rate of 1-5 ℃/min, and naturally cooling to room temperature to obtain a lithium-rich manganese-based layered cathode material;
s3, preparing an oxygen vacancy lithium-rich manganese-based layered positive electrode material:
and (3) uniformly dispersing the lithium-rich manganese-based layered positive electrode material obtained in the step (S2) in a quartz boat, placing the quartz boat in a tube furnace, continuously introducing argon for 10-60 minutes before starting heating, then heating to 800 ℃ at the speed of 1-5 ℃/min, and preserving heat for 600 minutes to obtain the lithium-rich manganese-based layered positive electrode material containing oxygen vacancies.
As a further description of the above technical solution:
the metal ion mixed solution comprises the following specific mixture ratio: the metal salt of cobalt, the metal salt of nickel and the metal salt of manganese are as follows according to the molar ratio of metal ions: the metal salt of nickel, the metal salt of cobalt, the metal salt of manganese, (0.1-0.8), (0-0.4) and (0.1-0.9) are added so that the sum of the molar numbers of the three metal salts is less than or equal to 1 and the total molar concentration of metal ions is 1-3 mol/L.
As a further description of the above technical solution:
the metal salt of cobalt is CoSO4·7H2O、Co(NO3)2·6H2O、CoCl2·6H2O or Co (Ac)2·4H2O。
As a further description of the above technical solution:
the molar ratio of the precipitant solution to the metal ion mixed solution in the step 2) is as follows: and (3) a precipitant solution, namely a metal ion mixed solution which is 1 (0.7-2).
As a further description of the above technical solution:
the metal salt of nickel is NiSO4·6H2O、Ni(NO3)2·6H2O、NiCl2·6H2O or Ni (Ac)2·4H2O。
As a further description of the above technical solution:
the metal salt of manganese is MnSO4·H2O、Mn(NO3)2·4H2O、MnCl2·4H2O or Mn (Ac)2·4H2O。
As a further description of the above technical solution:
the precipitant is NaOH or Na2CO3、NaHCO3、(NH4)2CO3Or NH4HCO3Any one of them.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. in the method for preparing the oxygen vacancy lithium-rich manganese-based layered anode material by argon treatment, series materials with different oxygen vacancy concentrations are prepared by a direct heating method, namely argon and the lithium-rich manganese-based layered anode material are directly heated, and oxygen vacancies with different concentrations are successfully generated on the surface of the lithium-rich manganese-based layered anode material by changing the proportion of argon to raw materials, the heating time and the like.
2. Compared with the same oxygen-free vacancy-containing material, the oxygen-vacancy-containing lithium-rich manganese-based layered cathode material prepared by the method has the advantages that the battery performance such as the battery cycling stability, the multiplying power and the like is greatly improved, and the precipitation of surface oxygen and the voltage attenuation are simultaneously inhibited.
3. According to the preparation method, the oxygen vacancy lithium-rich manganese-based anode material is prepared through a simple heating method, the used argon is easy to obtain, the raw materials required by reactants are easy to obtain and low in cost, special protection is not needed in the production process, the reaction conditions are easy to control, and the obtained product has the advantages of high yield, good result repeatability and the like. The method has the advantages of simple synthesis process, high production efficiency and lower production cost, and is suitable for large-scale production.
Drawings
FIG. 1 shows that oxygen vacancy-containing lithium-rich manganese-based layered cathode material obtained by heating the anode material for 5 hours after the anode material is heated to 400 ℃ under the condition of argon flow of 30mL/min and the heating rate of 1 ℃/min is 0.1C,0.2C,0.5C,1℃,2C, 5C and 10C (1℃ is 250 mAg)-1) A discharge specific capacity cycle comparison graph under current density;
FIG. 2 shows that the oxygen vacancy-containing lithium-rich manganese-based layered positive electrode material obtained by heating the mixture for 5 hours after the temperature rise speed of 1 ℃/min is increased to 400 ℃ in an argon flow of 30mL/min and the untreated lithium-rich manganese-based layered positive electrode material is at 0.2C (1℃: 250 mAg)-1) A discharge specific capacity cycle comparison graph under current density;
FIG. 3 shows that the oxygen vacancy-containing lithium-rich manganese-based layered positive electrode material obtained by heating the anode material at 30mL/min argon flow and a heating rate of 1 ℃/min to 400 ℃ for 5 hours and the untreated lithium-rich manganese-based layered positive electrode material are at 0.2C (1℃: 250 mAg)-1) Voltage decay versus cycle plot at current density.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a modification method of a lithium-rich oxide cathode material, which directly heats a lithium-rich manganese-based cathode material under an argon atmosphere to generate oxygen vacancies, and comprises the following steps:
(1) preparing a carbonate precursor:
dissolving cobalt metal salt, nickel metal salt and manganese metal salt in pure water, wherein the cobalt metal salt, the nickel metal salt and the manganese metal salt are prepared according to the molar ratio of metal ions: a metal salt of nickel, a metal salt of cobalt, a metal salt of manganese, (0.1-0.8), (0-0.4) and (0.1-0.9), wherein the sum of the molar numbers of the three metal salts is less than or equal to 1, and the total molar concentration of metal ions is 1-3 mol/L to obtain a metal ion mixed solution; preparing a carbonate precipitant solution with the molar concentration of 1-3 mol/L, and adding the precipitant solution into the metal ion mixed solution under magnetic stirring, wherein the molar ratio of the added solution is as follows: and (3) a precipitant solution, namely (0.7-2) a metal ion mixed solution, generating a coprecipitation product, stirring for 6-18 hours, performing centrifugal separation on the coprecipitation product, respectively washing the precipitate with deionized water for three times and absolute ethyl alcohol for two times, and drying the precipitate in an oven at 80 ℃ for 24 hours to obtain a carbonate precursor, wherein the molecular formula of the carbonate precursor is as follows: (Mn)0.1～ 0.9Ni0.1～0.8Co0～0.5)1.25CO3·2H2O；
(2) Preparing a lithium-rich manganese-based layered cathode material:
mixing the carbonate precursor obtained in the step (1) with LiOH & H2O or Li2CO3Mixing according to the molar ratio of 1 (1-2), fully grinding to ensure that the particle diameter is 0.5-5 um, uniformly mixing, placing in a muffle furnace, and heating at the rate of 1-5 ℃/min to 700-10%Calcining for 6-24 hours at 00 ℃, and naturally cooling to room temperature to obtain the lithium-rich manganese-based layered cathode material;
(3) preparing an oxygen vacancy lithium-rich manganese-based layered cathode material:
and (3) uniformly dispersing the lithium-rich manganese-based layered positive electrode material obtained in the step (2) in a quartz boat, and placing the quartz boat in a tube furnace. Argon is continuously introduced for 10-60 minutes before the heating is started, then the temperature is raised to 800 ℃ at the speed of 1-5 ℃/min, and the temperature is maintained for 600 minutes. And obtaining the lithium-rich manganese-based layered cathode material containing oxygen vacancies.
The metal salt of cobalt is CoSO4·7H2O、Co(NO3)2·6H2O、CoCl2·6H2O or Co (Ac)2·4H2O。
The metal salt of nickel is NiSO4·6H2O、Ni(NO3)2·6H2O、NiCl2·6H2O or Ni (Ac)2·4H2O。
The metal salt of manganese is MnSO4·H2O、Mn(NO3)2·4H2O、MnCl2·4H2O or Mn (Ac)2·4H2O。
The precipitant is NaOH or Na2CO3、NaHCO3、(NH4)2CO3Or NH4HCO3Any of the above.
An embodiment of the method of the invention is described below:
the first embodiment is as follows:
(1) the metal salt of cobalt, CoSO4·7H2Metal salts of O and Ni NiSO4·6H2MnSO metal salt of O and Mn4·H2Dissolving O in 100mL of water according to a molar ratio of 0.13:0.13:0.54 to ensure that the total molar concentration of metal ions is 2mol/L to obtain a metal ion mixed solution; preparing Na with the molar concentration of 2mol/L2CO3Adding 50mL of solution of the precipitant into the mixed solution of the metal ions under magnetic stirring to generate precipitates, stirring for 12 hours, performing centrifugal separation, and respectively using deionized water and deionized waterWashing the precipitate with water and ethanol for 2 times, and drying the precipitate in an oven at 80 ℃ for 12 hours to obtain a carbonate precursor, wherein the molecular formula of the carbonate precursor is as follows: (Ni)0.13Co0.13Mn0.54)1.25CO3·2H2O。
(2) Mixing the carbonate precursor obtained in the step (1) with LiOH & H2O or Li2CO3Fully grinding and uniformly mixing the materials according to the molar ratio of 1:1.08, placing the materials in a muffle furnace, calcining the materials at 900 ℃ for 12 hours at the heating rate of 3-5 ℃/min, and naturally cooling the materials to room temperature to obtain the corresponding lithium-rich manganese-based layered cathode material of the lithium ion battery.
(3) And (3) uniformly dispersing 1-6g of the lithium-rich manganese-based layered positive electrode material obtained in the step (2) in a quartz boat, and placing the quartz boat in a tube furnace. Argon is continuously introduced for 10-60 minutes before heating is started, then the temperature is raised to 300 ℃ at the speed of 1-5 ℃/min, and the temperature is preserved for 300 minutes. And obtaining the lithium-rich manganese-based layered cathode material containing oxygen vacancies.
Example two:
(1) the metal salt NiCl of nickel2·6H2Metal salts of O and Mn, MnCl2·4H2Dissolving O in 100mL of water according to a molar ratio of 0.2:0.6 to ensure that the total molar concentration of metal ions is 2mol/L to obtain a metal ion mixed solution; preparing 50mL of NaOH solution with the molar concentration of 2mol/L, adding the precipitant solution into the metal ion mixed solution under magnetic stirring to generate a precipitate, stirring for 8 hours, performing centrifugal separation, respectively washing the precipitate with deionized water and absolute ethyl alcohol for 2 times, and drying the precipitate in an oven at 80 ℃ for 12 hours to obtain a hydroxide precursor, wherein the molecular formula of the hydroxide precursor is as follows: ni0.2Mn0.6(OH)1.6·2H2O。
(2) The hydroxide precursor obtained in the step (1) and LiOH & H2O or Li2CO3Fully grinding and uniformly mixing the materials according to the molar ratio of 1:1.05, placing the materials in a muffle furnace, calcining the materials at 900 ℃ for 12 hours at the heating rate of 3-5 ℃/min, and naturally cooling the materials to room temperature to obtain the corresponding lithium-rich manganese-based layered cathode material of the lithium ion battery.
(3) And (3) uniformly dispersing 1-6g of the lithium-rich manganese-based layered positive electrode material obtained in the step (2) in a quartz boat, and placing the quartz boat in a tube furnace. Argon is continuously introduced for 10-60 minutes before heating is started, then the temperature is raised to 400 ℃ at the speed of 1-5 ℃/min, and the temperature is preserved for 300 minutes. And obtaining the lithium-rich manganese-based layered cathode material containing oxygen vacancies.
Example three:
(1) metal salt of nickel Ni (NO)3)2·6H2Metal salts of O and manganese, Mn (NO)3)2·4H2Dissolving O in 100mL of water according to a molar ratio of 0.2:0.6 to ensure that the total molar concentration of metal ions is 2mol/L to obtain a metal ion mixed solution; preparing NaHCO with the molar concentration of 2mol/L3Adding the precipitant solution into the metal ion mixed solution under magnetic stirring to generate a precipitate, stirring for 8 hours, performing centrifugal separation, respectively washing the precipitate with deionized water and absolute ethyl alcohol for 2 times, and drying the precipitate in an oven at 80 ℃ for 12 hours to obtain a bicarbonate precursor, wherein the molecular formula of the bicarbonate precursor is as follows: ni0.2Mn0.6(HCO3)1.6·2H2O。
(2) Reacting the bicarbonate precursor obtained in the step (1) with LiOH & H2O or Li2CO3Fully grinding and uniformly mixing the materials according to the molar ratio of 1:1.05, placing the materials in a muffle furnace, calcining the materials at 900 ℃ for 12 hours at the heating rate of 3-5 ℃/min, and naturally cooling the materials to room temperature to obtain the corresponding lithium-rich manganese-based layered cathode material of the lithium ion battery.
(3) And (3) uniformly dispersing 1-6g of the lithium-rich manganese-based layered positive electrode material obtained in the step (2) in a quartz boat, and placing the quartz boat in a tube furnace. Argon is continuously introduced for 10-60 minutes before heating is started, then the temperature is raised to 600 ℃ at the speed of 1-5 ℃/min, and the temperature is preserved for 200 minutes. And obtaining the lithium-rich manganese-based layered cathode material containing oxygen vacancies.
Example four:
(1) a metal salt of nickel Ni (Ac)2·4H2Metal salts of O and manganese Mn (Ac)2·4H2O in a molar ratio of 0.2:0.6Dissolving the mixture into 100mL of water in proportion to ensure that the total molar concentration of metal ions is 2mol/L to obtain a metal ion mixed solution; preparing (NH) with the molar concentration of 2mol/L4)2CO3Adding the precipitant solution into the metal ion mixed solution under magnetic stirring to generate a precipitate, stirring for 8 hours, performing centrifugal separation, respectively washing the precipitate with deionized water and absolute ethyl alcohol for 2 times, and drying the precipitate in an oven at 80 ℃ for 12 hours to obtain an acetate precursor, wherein the molecular formula of the acetate precursor is as follows: (Ni)0.2Mn0.6)1.25CO3·2H2O。
(2) Mixing the acetate precursor obtained in the step (1) with LiOH & H2O or Li2CO3Fully grinding and uniformly mixing the materials according to the molar ratio of 1:1.05, placing the materials in a muffle furnace, calcining the materials at 900 ℃ for 12 hours at the heating rate of 3-5 ℃/min, and naturally cooling the materials to room temperature to obtain the corresponding lithium-rich manganese-based layered cathode material of the lithium ion battery.
(3) And (3) uniformly dispersing 1-6g of the lithium-rich manganese-based layered positive electrode material obtained in the step (2) in a quartz boat, and placing the quartz boat in a tube furnace. Argon is continuously introduced for 10-60 minutes before heating is started, then the temperature is raised to 600 ℃ at the speed of 1-5 ℃/min, and the temperature is preserved for 300 minutes. And obtaining the lithium-rich manganese-based layered cathode material containing oxygen vacancies.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A method for modifying a lithium-rich oxide cathode material is characterized in that an oxygen vacancy is generated by adopting a direct heating argon method, and the method comprises the following steps:
s1, preparation of a carbonate precursor:
1) dissolving cobalt metal salt, nickel metal salt and manganese metal salt in pure water to obtain a metal ion mixed solution;
2) preparing a carbonate precipitant solution with the molar concentration of 1-3 mol/L, and adding the precipitant solution into the metal ion mixed solution under magnetic stirring to generate a coprecipitation product;
3) stirring the coprecipitation product for 6-18 hours, then carrying out centrifugal separation on the coprecipitation product, and respectively washing the precipitate with deionized water for three times and absolute ethyl alcohol for two times;
4) and (3) drying the precipitate in an oven at 80 ℃ for 24 hours to obtain a carbonate precursor, wherein the molecular formula of the carbonate precursor is as follows: (Mn)0.1～0.9Ni0.1～0.8Co0～0.5)1.25CO3·2H2O；
S2, preparing a lithium-rich manganese-based layered positive electrode material:
the carbonate precursor obtained in S1 was reacted with LiOH. H2O or Li2CO3Mixing according to the molar ratio of 1 (1-2), and fully grinding to ensure that the particle diameter is 0.5-5 um; uniformly mixing, placing in a muffle furnace, calcining at 700-1000 ℃ for 6-24 hours at a heating rate of 1-5 ℃/min, and naturally cooling to room temperature to obtain a lithium-rich manganese-based layered cathode material;
s3, preparing an oxygen vacancy lithium-rich manganese-based layered positive electrode material:
and (3) uniformly dispersing the lithium-rich manganese-based layered positive electrode material obtained in the step (S2) in a quartz boat, placing the quartz boat in a tube furnace, continuously introducing argon for 10-60 minutes before starting heating, then heating to 800 ℃ at the speed of 1-5 ℃/min, and preserving heat for 600 minutes to obtain the lithium-rich manganese-based layered positive electrode material containing oxygen vacancies.
2. The method for modifying the lithium-rich oxide cathode material according to claim 1, wherein the specific ratio of the metal ion mixed solution is as follows: the metal salt of cobalt, the metal salt of nickel and the metal salt of manganese are as follows according to the molar ratio of metal ions: the metal salt of nickel, the metal salt of cobalt, the metal salt of manganese, (0.1-0.8), (0-0.4) and (0.1-0.9) are added so that the sum of the molar numbers of the three metal salts is less than or equal to 1 and the total molar concentration of metal ions is 1-3 mol/L.
3. The method for modifying a lithium-rich oxide cathode material according to claim 2, wherein the cobalt metal salt is CoSO4·7H2O、Co(NO3)2·6H2O、CoCl2·6H2O or Co (Ac)2·4H2O。
4. The method for modifying the lithium-rich oxide cathode material according to claim 1, wherein the molar ratio of the precipitant solution to the metal ion mixed solution in the step 2) is as follows: and (3) a precipitant solution, namely a metal ion mixed solution which is 1 (0.7-2).
5. The method for modifying a lithium-rich oxide cathode material as claimed in claim 1, wherein the metal salt of nickel is NiSO4·6H2O、Ni(NO3)2·6H2O、NiCl2·6H2O or Ni (Ac)2·4H2O。
6. The method for modifying a lithium-rich oxide cathode material as claimed in claim 1, wherein the metal salt of manganese is MnSO4·H2O、Mn(NO3)2·4H2O、MnCl2·4H2O or Mn (Ac)2·4H2O。
7. The method for modifying a lithium-rich oxide cathode material as claimed in claim 1, wherein the precipitant is NaOH or Na2CO3、NaHCO3、(NH4)2CO3Or NH4HCO3Any one of them.
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