CN113889618A - Hydrophobic anode material modified by organic silicide and preparation method thereof - Google Patents
Hydrophobic anode material modified by organic silicide and preparation method thereof Download PDFInfo
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- 239000010405 anode material Substances 0.000 title claims abstract description 55
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 41
- 229910021332 silicide Inorganic materials 0.000 title claims abstract description 17
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 37
- 239000010406 cathode material Substances 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000011258 core-shell material Substances 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 4
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical group CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229910018632 Al0.05O2 Inorganic materials 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- 239000000463 material Substances 0.000 description 20
- 238000005303 weighing Methods 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000006467 substitution reaction 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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 belongs to the technical field of lithium ion battery anode materials, and particularly relates to an organosilicate-modified hydrophobic anode material and a preparation method thereof. The hydrophobic anode material is obtained by modifying a matrix anode material through an organic silicide, wherein the matrix anode material is of a core-shell structure and is prepared through a coprecipitation-high-temperature sintering method. The preparation method of the hydrophobic anode material comprises the following steps: carrying out Mo/Al element co-doping, deionized water washing and Ce oxide coating treatment on a matrix anode material; adding an organic silicide into a solvent to form a uniform solution; the volume ratio of the organic silicide to the solvent is 1 (100-300); adding the treated matrix cathode material into the uniform solution, and stirring at a constant speed for 0.5-6 h to obtain a solid-liquid mixed solution; and carrying out post-treatment to obtain the hydrophobic cathode material. The method is simple and easy to control, and can effectively solve the problem that trace residual alkali on the surface of the anode material adsorbs water.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to an organosilicate-modified hydrophobic anode material and a preparation method thereof.
Background
In recent years, with the rigorous requirements of some electric energy systems on high specific capacity, the positive electrode material gradually develops towards high nickel, and the aim is to increase the specific capacity of the material by increasing the nickel content, so that the material meets the performance index requirement of high specific capacity. However, the increase of the nickel content increases the total alkali amount on the surface of the material, i.e. the surface has more lithium residues. The lithium residue is easy to absorb moisture and carbon dioxide in the air to form Li2CO3And LiOH, which increases the total alkali content on the surface of the material, affects the cycle stability and long storage performance in humid environments of the positive electrode material, and results in a high nickel positive electrode material being more sensitive to moisture.
In general, most of lithium residues on the surface of the high-nickel cathode material are solved by a water washing process and a coating technology. The water washing process can wash away most of lithium residues on the surface of the material by washing; the coating technology can treat the surface of the material after being washed, so that the coating layer can inhibit the corrosion of electrolyte on one hand, and can inhibit phase change on the other hand, and the interface stability of the material is improved. However, a small amount of lithium residues still exist on the surface of the positive electrode material after being washed and coated, the surface is hydrophilic, and when the positive electrode material is exposed in air or in a humid environment, the positive electrode material is very easy to absorb moisture in the air, so that certain irreversible influence is caused on the material performance and the electrode manufacturing.
In order to solve the problems, a method of performing hydrophobic treatment on the surface of a material is adopted at present, and the adsorption of lithium residues on the surface of a nickel-rich material to moisture is inhibited. However, the existing research process is complex, the hydrophobic research is mostly carried out on the basis of the conventional cathode material, and the cycle stability and the long storage performance in a humid environment of the hydrophobically modified core-shell structure cathode material are not researched.
Disclosure of Invention
In order to solve the problems, the invention provides an organosilicate-modified hydrophobic anode material and a preparation method thereof, wherein the core-shell structure anode material is used as a matrix, and the surface of the matrix anode material is modified by organosilicate to form a hydrophobic protective film which can block the adsorption of the surface of the material on moisture; meanwhile, the corrosion of HF in the electrolyte to the positive plate is inhibited to a certain extent, and the interface stability of the material and the long-term storage performance in a humid environment are improved. The method is simple and easy to control, and can effectively solve the problem that trace residual alkali on the surface of the anode material adsorbs water.
In order to achieve the purpose, the technical scheme of the invention is as follows:
an organosilicate-modified hydrophobic anode material is obtained by modifying a matrix anode material through organosilicate, wherein the matrix anode material is of a core-shell structure, and the molecular formula of a core body is LiNi0.86Co0.11Al0.03O2And the molecular formula of the shell layer is LiNi0.84Co0.11Al0.05O2。
Further, the matrix cathode material is prepared by a coprecipitation-high temperature sintering method.
Further, the preparation method of the hydrophobic anode material modified by the organic silicide comprises the following steps:
s1, co-doping the matrix anode material with Mo/Al elements, washing with deionized water, and coating with Ce oxide;
s2, adding the organic silicide into the solvent to form a uniform solution; the volume ratio of the organic silicide to the solvent is 1 (100-300);
s3, adding the matrix cathode material treated in the S1 into the uniform solution of the S2, and stirring at a constant speed for 0.5-6 hours to obtain a solid-liquid mixed solution;
s4, post-processing to obtain a hydrophobic anode material; the post-treatment comprises filtering and vacuum drying, wherein the drying temperature is 40-120 ℃, and the drying time is 6-15 h; the vacuum degree is (-0.1-0.08) MPa, and the hydrophobic anode material is obtained.
Further, the organic silicide in S2 is octadecyltrichlorosilane; the solvent is one or more of alkanes, ketones, pyridine and ethers.
The invention has the advantages and positive effects that:
1. according to the hydrophobic anode material, the organic silicide is adopted to modify the matrix anode material, so that a hydrophobic protective film is formed on the surface of the material, the adsorption of the anode material to water in the air can be effectively blocked, the corrosion of electrolyte is reduced, and the interface stability and the long storage performance of the material in a humid environment are improved.
2. The organic silicon compound adopted in the hydrophobic treatment is easy to obtain, low in cost and non-toxic, and can be produced in a large scale.
3. The preparation method of the hydrophobic anode material provided by the invention has the advantages of simple process, low cost and good economic prospect.
Drawings
FIG. 1 is a molecular structural formula of octadecyltrichlorosilane.
Detailed Description
For a further understanding of the invention, its nature and utility, reference should be made to the following examples, which are set forth in the following detailed description, taken in conjunction with the accompanying drawings, in which:
the invention discloses an organosilicate-modified hydrophobic anode material which is obtained by modifying a matrix anode material through an organosilicate, wherein the matrix anode material is of a core-shell structure, and the molecular formula of a core body is LiNi0.86Co0.11Al0.03O2And the molecular formula of the shell layer is LiNi0.84Co0.11Al0.05O2(ii) a The matrix positive electrode material is prepared by a coprecipitation-high temperature sintering method; the matrix anode material is subjected to doping, washing and coating treatment, wherein the doping is Mo/Al element co-doping, the washing adopts deionized water washing, and the coating is a Ce oxide bagAnd (4) covering.
The invention relates to a preparation method of a hydrophobic anode material modified by organosilicon compounds, which comprises the following steps:
s1, co-doping the matrix anode material with Mo/Al elements, washing with deionized water, and coating with Ce oxide;
s2, adding the organic silicide into the solvent to form a uniform solution; the organic silicide is Octadecyltrichlorosilane (OTS), and the molecular structural formula is shown in figure 1; the solvent is one or more of alkanes, ketones, pyridine and ethers, preferably one or more of n-hexane, cyclohexane, acetone, pyridine, propylene glycol ethyl ether and ethyl ether, and more preferably one or more of n-hexane, cyclohexane and propylene glycol ethyl ether. Preferably, the volume ratio of the organic silicide to the solvent is 1 (100-300).
S3, adding the matrix anode material into the mixed uniform solution, and stirring at a constant speed for 0.5-6 h to obtain a solid-liquid mixed solution;
s4, post-processing to obtain a hydrophobic anode material; the post-treatment comprises filtering and vacuum drying, wherein the drying temperature is 40-120 ℃, the drying time is 6-15 h, and the vacuum degree is (-0.1-0.08) MPa, so that the hydrophobic anode material is obtained.
Example 1
A preparation method of a hydrophobic anode material modified by organosilicate comprises the following steps:
s1, co-doping the matrix anode material with Mo/Al elements, washing with deionized water, and coating with Ce oxide;
s2, weighing the octadecyl trichlorosilane and the normal hexane in parts, preparing 200mL of normal hexane solution of the octadecyl trichlorosilane with the volume ratio of 1:200, and uniformly stirring;
s3, weighing 100g of matrix cathode material, slowly adding the cathode material into n-hexane solution of octadecyl trichlorosilane, and uniformly stirring for 3 hours to obtain a solid-liquid mixed solution;
s4, filtering the obtained solid-liquid mixed solution by adopting a filtering device, transferring the filtered solid filter cake into a vacuum oven to be dried for 12 hours at the temperature of 80 ℃, and obtaining the hydrophobic anode material when the vacuum degree is (-0.1 to-0.08) MPa.
Example 2
S1, co-doping the matrix anode material with Mo/Al elements, washing with deionized water, and coating with Ce oxide;
s2, respectively weighing octadecyl trichlorosilane and normal hexane, preparing 200mL normal hexane solution of octadecyl trichlorosilane with the volume ratio of 1:300, and uniformly stirring;
s3, weighing 100g of matrix cathode material, slowly adding the cathode material into n-hexane solution of octadecyl trichlorosilane, and uniformly stirring for 3 hours to obtain a solid-liquid mixed solution;
s4, filtering the obtained solid-liquid mixed solution by adopting a filtering device, transferring the filtered solid filter cake into a vacuum oven to be dried for 12 hours at the temperature of 80 ℃, and obtaining the hydrophobic anode material when the vacuum degree is (-0.1 to-0.08) MPa.
Example 3
S1, co-doping the matrix anode material with Mo/Al elements, washing with deionized water, and coating with Ce oxide;
s2, respectively weighing the octadecyl trichlorosilane and the normal hexane, preparing 200mL of normal hexane solution of the octadecyl trichlorosilane with the volume ratio of 1:100, and uniformly stirring.
S3, weighing 100g of matrix cathode material, slowly adding the cathode material into n-hexane solution of octadecyl trichlorosilane, and uniformly stirring for 3 hours to obtain a solid-liquid mixed solution.
S4, filtering the obtained solid-liquid mixed solution by adopting a filtering device, transferring the filtered solid filter cake into a vacuum oven to be dried for 12 hours at the temperature of 80 ℃, and obtaining the hydrophobic anode material when the vacuum degree is (-0.1 to-0.08) MPa.
Example 4
S1, co-doping the matrix anode material with Mo/Al elements, washing with deionized water, and coating with Ce oxide;
s2, respectively weighing the octadecyl trichlorosilane and the normal hexane, preparing 200mL of normal hexane solution of the octadecyl trichlorosilane with the volume ratio of 1:200, and uniformly stirring.
S3, weighing 100g of matrix cathode material, slowly adding the cathode material into n-hexane solution of octadecyl trichlorosilane, and uniformly stirring for 0.5h to obtain a solid-liquid mixed solution.
S4, filtering the obtained solid-liquid mixed solution by adopting a filtering device, transferring the filtered solid filter cake into a vacuum oven to be dried for 12 hours at the temperature of 80 ℃, and obtaining the hydrophobic anode material when the vacuum degree is (-0.1 to-0.08) MPa.
Example 5
S1, co-doping the matrix anode material with Mo/Al elements, washing with deionized water, and coating with Ce oxide;
s2, respectively weighing the octadecyl trichlorosilane and the normal hexane, preparing 200mL of normal hexane solution of the octadecyl trichlorosilane with the volume ratio of 1:200, and uniformly stirring.
S3, weighing 100g of matrix cathode material, slowly adding the cathode material into n-hexane solution of octadecyl trichlorosilane, and uniformly stirring for 6 hours to obtain a solid-liquid mixed solution.
S4, filtering the obtained solid-liquid mixed solution by adopting a filtering device, transferring the filtered solid filter cake into a vacuum oven to be dried for 12 hours at the temperature of 80 ℃, and obtaining the hydrophobic anode material when the vacuum degree is (-0.1 to-0.08) MPa.
Comparative example
Comparative example 1
In this example, the matrix positive electrode material was used as a control without performing hydrophobic treatment.
Comparative example 2
S1, weighing the n-hexane solution according to the mass ratio of the matrix cathode material to the n-hexane in the embodiment 1.
S2, weighing 100g of matrix cathode material, slowly adding the matrix cathode material into the n-hexane solution, and stirring at a low speed for 2 hours to obtain a solid-liquid mixed solution.
S3, filtering the obtained solid-liquid mixed solution by adopting a filtering device, transferring the filtered solid filter cake into a vacuum oven to be dried for 12 hours at the temperature of 80 ℃, and obtaining the hydrophobic anode material when the vacuum degree is (-0.1 to-0.08) MPa.
Examples of the experiments
Experimental example 1
The CR2430 button cell was fabricated by using the positive electrode material of example, comparative example 1 and comparative example 2, and the negative electrode material of lithium sheet, respectively. The manufacturing method of the CR2430 button cell comprises the following steps:
5.4g of positive electrode material, 0.3g of acetylene black and 5.0g of PVDF solution are weighed respectively according to the mass ratio of 90:5:5, then a proper amount of N-methyl-2 pyrrolidone is added, and the mixture is placed on a magnetic stirrer to be uniformly mixed to obtain slurry. And then coating the slurry on aluminum foil paper, drying for 3h, rolling, slicing and weighing. Then the prepared pole piece is transferred into a glove box, and the assembly sequence is as follows: the negative electrode shell, the elastic sheet, the gasket, the metal lithium sheet, the diaphragm, the positive electrode sheet and the positive electrode shell are assembled into the CR2430 button cell.
(1) Test for cycling stability
And (3) carrying out 1C cycle 60-circle performance test on the assembled CR2430 button cell at the normal temperature within the voltage range of 2.5-4.25V, wherein the test results are shown in Table 1.
TABLE 1 CR2430 button cell cycle test data at Normal temperature
As can be seen from table 1, compared with comparative examples 1 and 2, examples 1 to 5, which are cycled for 60 cycles at normal temperature, have higher retention rate of the cycling capacity, because the hydrophobic protective film formed on the surface of the material plays a positive role in the stability of the material interface, the damage to the interface in the material cycling process can be reduced to a certain extent, and thus the retention rate of the cycling capacity of the material is greatly improved.
(2) Long storage Performance test in humid Environment
And (3) performing cyclic two-circle activation charging on the assembled CR2430 button cell in a voltage range of 2.5-4.25V at normal temperature, placing the button cell in a humid environment (humidity is 70 +/-5%) for long-term storage testing, and taking out the button cell for discharging after 30 days. The test results are shown in table 2.
TABLE 2 specific discharge capacity recovery test data after long storage in humid environment
As can be seen from Table 2, the recovery rate of the specific discharge capacity of the anode material without hydrophobic treatment is low, and after hydrophobic treatment, the recovery rate of the specific discharge capacity can reach 95.08%, and the improvement is obvious. The hydrophobic protective film formed on the surface of the material can effectively improve the interface stability of the material and inhibit the adsorption of moisture in humid air, thereby improving the specific discharge capacity recovery rate after long-term storage in a humid environment.
The embodiments described herein are only some, and not all, embodiments of the invention. Based on the above explanations and guidance, those skilled in the art can make modifications, improvements, substitutions, and the like on the embodiments based on the present invention and examples, but all other embodiments obtained without innovative research fall within the scope of the present invention.
Claims (4)
1. An organosilicate-modified hydrophobic anode material is characterized in that: is obtained by modifying a matrix anode material through an organic silicide, wherein the matrix anode material is of a core-shell structure, and the molecular formula of a core body is LiNi0.86Co0.11Al0.03O2And the molecular formula of the shell layer is LiNi0.84Co0.11Al0.05O2。
2. The organosilicate-modified hydrophobic positive electrode material according to claim 1, wherein: the matrix cathode material is prepared by a coprecipitation-high temperature sintering method.
3. The method for preparing the organosilicate-modified hydrophobic positive electrode material according to claim 2, comprising the steps of:
s1, co-doping the matrix anode material with Mo/Al elements, washing with deionized water, and coating with Ce oxide;
s2, adding the organic silicide into the solvent to form a uniform solution; the volume ratio of the organic silicide to the solvent is 1 (100-300);
s3, adding the matrix cathode material treated in the S1 into the uniform solution of the S2, and stirring at a constant speed for 0.5-6 hours to obtain a solid-liquid mixed solution;
s4, post-processing to obtain a hydrophobic anode material; the post-treatment comprises filtering and vacuum drying, wherein the drying temperature is 40-120 ℃, and the drying time is 6-15 h; the vacuum degree is (-0.1-0.08) MPa, and the hydrophobic anode material is obtained.
4. The method for producing an organosilicate-modified hydrophobic positive electrode material according to claim 2, wherein: the organic silicide is octadecyl trichlorosilane; the solvent is one or more of alkanes, ketones, pyridine and ethers.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102770991A (en) * | 2010-02-24 | 2012-11-07 | 日立麦克赛尔能源株式会社 | Positive electrode material, method of production therefor, positive electrode for nonaqueous rechargeable battery, and nonaqueous rechargeable battery |
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