CN115312750A - Preparation method of lithium battery electrode material - Google Patents
Preparation method of lithium battery electrode material Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920001817 Agar Polymers 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 239000011246 composite particle Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008272 agar Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 230000033558 biomineral tissue development Effects 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000004108 freeze drying Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 41
- 239000011572 manganese Substances 0.000 description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910001453 nickel ion Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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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
- 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
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Abstract
The invention discloses a preparation method of an electrode material of a lithium battery, which comprises the following steps: s1, preparing a graphene oxide dispersion liquid; s2, preparing MCO 3 (M = Mn + Ni) agar gel precursor; s3, preparing the micron-sized grape-shaped MnO-Ni @ C composite particles. The preparation method of the lithium battery electrode material disclosed by the invention adopts biomineralization combined with freeze drying and carbonization processes to prepare the MnO-Ni @ C electrode material with a grape-shaped structure; the double-carbon-layer grape-shaped structure of the MnO-Ni @ C electrode material and the Ni metal simple substance act together, so that the problems of overlarge volume expansion and low conductivity in the MnO circulating process are greatly relieved, and the problem of capacity change in the circulating process is successfully solved; mnO-NiThe Ni metal in the @ C electrode material participates in the reaction in the circulation process, thereby contributing partial capacity to the motor material and further preventing Mn 2+ Oxidation to higher valence state, and stable cycle performance.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a preparation method of a lithium battery electrode material.
Background
The MnO base material has the advantages of high theoretical specific capacity, low potential platform, high density, small circular polarization, environmental friendliness, large storage capacity, low cost and the like, so that the MnO base material becomes an attractive lithium ion battery cathode material. At present, a great deal of research work is directed to MnO-based electrode materials and better electrochemical properties are obtained. The compounding of MnO-based electrode materials and the nanocrystallization of the materials are two most effective strategies for improving the comprehensive electrochemical performance of the materials. The nano-preparation can shorten the diffusion distance of lithium ions, relieve the structural stress generated by the insertion/de-intercalation of the lithium ions, improve the reaction kinetics with a large specific surface, and thus significantly improve the performance of the battery. By introducing the carbon-based material, the conductivity of the material can be greatly improved, and the buffer active material can buffer large volume expansion in the circulating process, so that the MnO/C composite electrode material has excellent electrochemical performance.
However, mnO-based materials still have some problems that prevent their commercial use as electrode materials for lithium ion batteries, since Mn is present 2+ The state is unstable, and the material is easily oxidized into a higher valence state, so that the capacity of the material is unstable in the charging and discharging process.
Disclosure of Invention
Based on the Mn, mn is necessary to the existing MnO-based materials as the lithium battery motor materials 2+ The technical problem that the unstable capacity of the material is easy to cause in the charging and discharging process due to the unstable state is solved.
A preparation method of an electrode material of a lithium battery comprises the following steps:
s1, preparing graphene oxide dispersion liquid.
S2, preparing MCO 3 (M = Mn + Ni) agar gel precursor.
S3, preparing the micron-sized grape-shaped MnO-Ni @ C composite particles.
In one embodiment, the step S1 includes the following steps:
s11, adding 0.15-2.0g of graphene into a beaker filled with 300-400mL of deionized water, and carrying out ultrasonic treatment until the graphene is uniformly dispersed;
s12, adding 68.2-70 mu L of hydrazine hydrate (N) into the dispersion liquid 2 H 4 H 2 O), 1050. Mu.L of ammonia water (NHH) 2 O）；
S13, placing the beaker in a constant-temperature water bath kettle at the temperature of 80-95 ℃ and preserving heat for 1-1.5 hours.
In one embodiment, the step S2 includes the following steps:
s21, adding a certain amount of MnCl 2 And NiCl particles dissolved in 500mL of deionized water to prepare 0.4M MCl 2 (M = Mn + Ni) solution;
s22, calculating the using amount of graphene according to the mass of 0.3%, 0.6%, 0.9% and 1.2% of graphene in MnO, and adding the mass of the dispersion liquid to four portions of MCl 2 (M = Mn + Ni) solution;
s23, adding 6g of agar powder into each prepared solution, placing the solution into a constant-temperature heating magnetic stirrer, and heating and stirring the solution until the agar is completely dissolved until the solution is boiled;
s24, placing the boiled solution in a ventilation place to be cooled to room temperature, and enabling the solution to form a colloid state with a stable structure;
s25, adding 200mL1.2M ammonium bicarbonate solution serving as a carbon source to the upper layer of each colloidal gel, standing for 48 hours to obtain four MCO with different graphene contents 3 (M = Mn + Ni) agar gel precursor.
In one embodiment, the step S3 includes the following steps:
s31, mixing each portion of MCO 3 (M = Mn + Ni) agar gel precursor is cut into sheets, and the sheets are respectively put into a freeze dryer for low-temperature drying;
s32, drying four parts of MCO 3 And (M = Mn + Ni) carrying out heat treatment on the agar gel precursor at 700-850 ℃ under inert gas, wherein the heating rate is 5 ℃/min, and carrying out heat preservation for 5-6 hours to complete carbonization treatment.
In one embodiment, the MnCl in the step S21 is 2 And the proportion of NiCl particles is as follows: ni 1+ In mole number of Ni 1+ And Mn 2+ 0% of the total molar amount.
In one embodiment, the above stepsMnCl in step S21 2 And the proportion of NiCl particles is as follows: ni 1+ In mole number of Ni 1+ And Mn 2+ 5 percent of the total mole number.
In one embodiment, the MnCl in the step S21 is 2 And the proportion of NiCl particles is as follows: ni 1+ In mole number of Ni 1+ And Mn 2+ 10% of the total molar amount.
In one embodiment, the MnCl in the step S21 is 2 And the proportion of NiCl particles is as follows: ni 1+ In mole number of Ni 1+ And Mn 2+ 15% of the total molar number.
In one embodiment, after the step S32 is completed, when the mole number of the nickel ions respectively accounts for 0%, 5%, 10% and 15% of the total mole number of the nickel and manganese ions, the obtained products are respectively labeled as MnO-Ni0@ C, mnO-Ni5@ C, mnO-Ni10@ C and MnO-Ni15@ C.
The preparation method of the lithium battery electrode material adopts biomineralization combined with freeze drying and carbonization processes to prepare the MnO-Ni @ C electrode material with a grape-shaped structure. The double-carbon-layer grape-shaped structure of the MnO-Ni @ C electrode material and the Ni metal simple substance act together, so that the problems of overlarge volume expansion and low conductivity in the MnO circulation process are greatly relieved, and the problem of capacity change in the circulation process is successfully solved. Ni metal in the MnO-Ni @ C electrode material participates in the reaction in the circulating process, thereby contributing partial capacity to the motor material and further preventing Mn 2+ Oxidation to higher valence state, and stable cycle performance.
Drawings
FIG. 1 is a sample scan of MnO-Ni0 (a), mnO-Ni5 (b), mnO-Ni10 (c) and MnO-Ni15 (d) prepared by direct biomineralization;
FIG. 2 is an MCO prepared by the method for preparing an electrode material for a lithium battery in one embodiment 3 (M = Mn + Ni) X-ray diffraction pattern of agar precursor (a), and content of 5%, 10% and 15% NiCO 3 A scan of the precursor (b-d);
FIG. 3 is a scanned graph of MnO-Ni5@ C (a, b) and MnO-Ni5@ C (c, d) prepared by the method for preparing an electrode material for a lithium battery in one example;
FIG. 4 is a graph of cycle performance test results for an electrode material at a current density of 0.1A/g in one example: mnO @ C and MnO-Ni10@ C (a), mnO-Ni5@ C (b), mnO-Ni15@ C (c); 1.0A/g current density cycle performance test of the electrode material: mnO @ C and MnO-Ni10@ C (d).
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments accompanying figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, as those skilled in the art will recognize without departing from the spirit and scope of the present invention.
The invention discloses a preparation method of an electrode material of a lithium battery, which comprises the following steps:
s1, preparing a graphene oxide dispersion liquid.
S2, preparing MCO 3 (M = Mn + Ni) agar gel precursor.
S3, preparing the micron-sized grape-shaped MnO-Ni @ C composite particles.
Further, step S1 includes the steps of:
s11, adding 0.15-2.0g of graphene into a beaker filled with 300-400mL of deionized water, and carrying out ultrasonic treatment until the graphene is uniformly dispersed;
s12, adding 68.2-70 mu L of hydrazine hydrate (N) into the dispersion liquid 2 H 4 H 2 O), 1050. Mu.L of ammonia water (NHH) 2 O）；
S13, placing the beaker in a constant-temperature water bath kettle at the temperature of 80-95 ℃ and preserving heat for 1-1.5 hours.
Further, step S2 includes the steps of:
s21, adding a certain amount of MnCl 2 And NiCl particles dissolved in 500mL of deionized water to prepare 0.4M MCl 2 (M = Mn + Ni) solution;
s22, according to the mass of the graphene in MnO0.3%, 0.6%, 0.9% and 1.2% of the amount of graphene used, the mass of the dispersion being added to four parts of MCl 2 (M = Mn + Ni) solution;
s23, adding 6g of agar powder into each part of prepared solution, placing the solution in a constant-temperature heating magnetic stirrer, and heating and stirring the solution until the agar is completely dissolved until the solution is boiled;
s24, placing the boiled solution in a ventilation place to be cooled to room temperature, and enabling the solution to form a colloid state with a stable structure;
s25, adding 200mL1.2M ammonium bicarbonate solution serving as a carbon source to the upper layer of each colloidal gel, standing for 48 hours to obtain four MCO with different graphene contents 3 (M = Mn + Ni) agar gel precursor.
Further, step S3 includes the following steps:
s31, mixing each portion of MCO 3 Cutting (M = Mn + Ni) agar gel precursor into sheets, and respectively putting the sheets into a freeze dryer for low-temperature drying;
s32, drying four parts of MCO 3 And (M = Mn + Ni) carrying out heat treatment on the agar gel precursor at 700-850 ℃ under inert gas, wherein the heating rate is 5 ℃/min, and carrying out heat preservation for 5-6 hours to complete carbonization treatment.
Further, mnCl in step S21 2 And the proportion of NiCl particles is as follows: ni 1+ In mole number of Ni 1+ And Mn 2+ 0% of the total molar amount.
Further, mnCl in step S21 2 And the proportion of NiCl particles is as follows: ni 1+ In mole number of Ni 1+ And Mn 2+ 5% of the total mole number.
Further, mnCl in step S21 2 And the proportion of NiCl particles is as follows: ni 1+ In mole number of Ni 1+ And Mn 2+ 10% of the total molar amount.
Further, mnCl in step S21 2 And the proportion of NiCl particles is as follows: ni 1+ In mole number of Ni 1+ And Mn 2+ 15% of the total mole number.
Specifically, after step S32 is completed, when the mole number of nickel ions respectively accounts for 0%, 5%, 10% and 15% of the total mole number of nickel and manganese ions, the obtained products are respectively marked as MnO-Ni0@ C, mnO-Ni5@ C, mnO-Ni10@ C and MnO-Ni15@ C.
In this example, FIG. 1 illustrates the preparation of MCO by biomineralization with the addition of NiCl2 as a preliminary step 3 (M = Mn + Ni) agar gel precursor boiling the colloid, and scanning pictures of MnO-Ni0, mnO-Ni5, mnO-Ni10 and MnO-Ni15 samples prepared by precursor particles in an inert atmosphere. As shown in fig. 1, the precursor particles changed from cubic to ellipsoidal after the addition of nickel, and the spheroids became more pronounced as the amount of nickel added increased.
In this example, fig. 2a is the XRD spectrum of the precursor sample after biomineralization, freeze drying, and MCO can be observed by comparing peak positions 3 Is MnCO 3 With NiCO 3 And (4) forming. Lyophilized MCO 3 Scanning electron microscope picture of agar gel precursor, as shown in FIG. 2b-d, the precursor is oval, has a size of about 10 μm, and MCO is added with metallic nickel simple substance 3 The shape of the precursor is changed from spherical to ellipsoidal along with the increase of the concentration of the metallic nickel.
Referring to FIG. 3, in the present embodiment, the images of the scanning electron microscope and the transmission electron microscope show the micro-morphology of the MnO-Ni @ C composite material particles in detail. The rough result is: micron MnO units wrapped by the porous carbon network form grape-shaped cores inside the particles, and MnO is encapsulated in a thicker carbon shell to form a multi-layer carbon-coated structure. Nickel nanocrystalline with a grain size of about 200 nm. Through the synergistic effect of the multilayer carbon structure and the metallic nickel, the method provides various advantages for improving the electrochemical performance, ensures high lithium ion conductivity, shortens the diffusion path, increases the number of active sites and effectively relieves the large volume change of the MnO motor material in the circulating process. The result shows that the Ni-Mn-O system is an effective method for improving the MnO circulation stability.
Referring to FIG. 4, in this embodiment, the MnO-Ni10@ C motor material can achieve stable cycle performance after 200 cycles at 0.1A/g, the capacity thereof is maintained at 706mAh/g, no significant capacity reduction problem occurs during the whole cycle process, and the coulombic efficiency is maintained at above 99.5%. The reversible discharge capacity of the MnO-Ni10@ C motor material isThe first 54 turns were outside the MnO theoretical capacity range. The results indicate that Ni metal also participates in redox reactions during discharge-charge. Meanwhile, under the same test condition, the specific capacity of the MnO @ C micron cubic particle is increased from 552mAh/g to 975mAh/g in the 200-turn circulation process, and the MnO @ C micron cubic particle shows obvious capacity change. Capacity increase over long cycles is a common phenomenon for high performance transition metal oxide machines. In particular for MnO Mn during the cycle 2+ Are readily oxidized to higher valence states.
TABLE 1
Referring to table 1, table 1 lists the capacity change during cycling of some high performance transition metal oxide electrodes. After long-period circulation, the discharge capacity retention rate of the electrode material can reach more than 200%. In this work, the capacity increase during long cycling was successfully mitigated by introducing elemental Ni into the MnO/C composite.
In conclusion, the preparation method of the lithium battery electrode material disclosed by the invention adopts biomineralization combined with freeze drying and carbonization processes to prepare the MnO-Ni @ C electrode material with a grape-shaped structure. The double-carbon-layer grape-shaped structure of the MnO-Ni @ C electrode material and the Ni metal simple substance act together, so that the problems of overlarge volume expansion and low conductivity in the MnO circulating process are greatly relieved, and the problem of capacity change in the circulating process is successfully solved. Ni metal in the MnO-Ni @ C electrode material participates in the reaction in the circulating process, thereby contributing partial capacity to the motor material and further preventing Mn 2+ Oxidation to higher valence state, and stable cycle performance.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (8)
1. The preparation method of the electrode material of the lithium battery is characterized by comprising the following steps of:
s1, preparing a graphene oxide dispersion liquid;
s2, preparing MCO 3 (M = Mn + Ni) agar gel precursor;
s3, preparing the micron-sized grape-shaped MnO-Ni @ C composite particles.
2. The method for preparing an electrode material for a lithium battery as claimed in claim 1, wherein the step S1 comprises the steps of:
s11, adding 0.15-2.0g of graphene into a beaker filled with 300-400mL of deionized water, and carrying out ultrasonic treatment until the graphene is uniformly dispersed;
s12, adding 68.2-70 mu L of hydrazine hydrate (N) into the dispersion liquid 2 H 4 H 2 O), 1050. Mu.L of ammonia water (NHH) 2 O）；
S13, placing the beaker in a constant-temperature water bath kettle at the temperature of 80-95 ℃ and preserving heat for 1-1.5 hours.
3. The method for preparing an electrode material for a lithium battery as claimed in claim 2, wherein the step S2 comprises the steps of:
s21, adding a certain amount of MnCl 2 And NiCl particles dissolved in 500mL of deionized water to prepare 0.4M MCl 2 (M = Mn + Ni) solution;
s22, calculating the using amount of graphene according to the mass of 0.3%, 0.6%, 0.9% and 1.2% of graphene in MnO, and adding the mass of the dispersion liquid to four parts of MCl 2 (M = Mn + Ni) solution;
s23, adding 6g of agar powder into each prepared solution, placing the solution into a constant-temperature heating magnetic stirrer, and heating and stirring the solution until the agar is completely dissolved until the solution is boiled;
s24, placing the boiled solution in a ventilation place to be cooled to room temperature, and enabling the solution to form a colloid state with a stable structure;
s25, adding 200mL1.2M ammonium bicarbonate solution serving as a carbon source to the upper layer of each colloidal gel, standing for 48 hours to obtain four MCO with different graphene contents 3 (M = Mn + Ni) agar gel precursor.
4. The method for preparing an electrode material for a lithium battery as claimed in claim 3, wherein the step S3 comprises the steps of:
s31, mixing each portion of MCO 3 Cutting (M = Mn + Ni) agar gel precursor into sheets, and respectively putting the sheets into a freeze dryer for low-temperature drying;
s32, drying four parts of MCO 3 And (M = Mn + Ni) carrying out heat treatment on the agar gel precursor at 700-850 ℃ under inert gas, wherein the heating rate is 5 ℃/min, and carrying out heat preservation for 5-6 hours to complete carbonization treatment.
5. The method for preparing an electrode material for a lithium battery as claimed in claim 3, wherein the MnCl is used in the step S21 2 And the proportion of NiCl particles is as follows: ni 1+ In mole number of Ni 1+ And Mn 2+ 0% of the total molar amount.
6. The method for preparing an electrode material for a lithium battery as claimed in claim 3, wherein the MnCl is used in the step S21 2 And the proportion of NiCl particles is as follows: ni 1+ In mole number of Ni 1+ And Mn 2+ 5 percent of the total mole number.
7. The method for preparing an electrode material for a lithium battery as claimed in claim 3, wherein the MnCl is used in the step S21 2 And the proportion of NiCl particles is as follows: ni 1+ In mole number of Ni 1+ And Mn 2+ 10% of the total molar amount.
8. The method for preparing an electrode material for a lithium battery according to claim 3, wherein the MnCl is added in step S21 2 And the proportion of NiCl particles is as follows: ni 1+ In mole number of Ni 1+ And Mn 2+ 15% of the total mole number.
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| CN106981643A (en) * | 2017-05-23 | 2017-07-25 | 山东大学 | A kind of method that biogel carbonization prepares double-deck carbon coating manganous oxide electrode material |
| CN112427041A (en) * | 2019-08-26 | 2021-03-02 | 中国科学院理化技术研究所 | Nickel-based catalyst for preparing low-carbon olefin through photo-thermal catalytic carbon monoxide hydrogenation and preparation method and application thereof |
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| CN106981643A (en) * | 2017-05-23 | 2017-07-25 | 山东大学 | A kind of method that biogel carbonization prepares double-deck carbon coating manganous oxide electrode material |
| CN112427041A (en) * | 2019-08-26 | 2021-03-02 | 中国科学院理化技术研究所 | Nickel-based catalyst for preparing low-carbon olefin through photo-thermal catalytic carbon monoxide hydrogenation and preparation method and application thereof |
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