CN115784321A - Modified nickel cobalt lithium manganate positive electrode material and preparation method thereof - Google Patents
Modified nickel cobalt lithium manganate positive electrode material and preparation method thereof Download PDFInfo
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- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical class [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 23
- 229920001661 Chitosan Polymers 0.000 claims abstract description 96
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 38
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 239000011159 matrix material Substances 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 25
- -1 imidazole compound Chemical class 0.000 claims abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims abstract description 14
- 238000004108 freeze drying Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910000077 silane Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- PRJKNHOMHKJCEJ-UHFFFAOYSA-N imidazol-4-ylacetic acid Chemical compound OC(=O)CC1=CN=CN1 PRJKNHOMHKJCEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical group C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 claims description 5
- OKRROXQXGNEUSS-UHFFFAOYSA-N 1h-imidazol-1-ium-1-carboxylate Chemical compound OC(=O)N1C=CN=C1 OKRROXQXGNEUSS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000005917 acylation reaction Methods 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 3
- 230000006196 deacetylation Effects 0.000 claims description 3
- 238000003381 deacetylation reaction Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000013557 residual solvent Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000010406 cathode material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
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- 238000007605 air drying Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 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
- 125000003277 amino group Chemical group 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
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- 230000009977 dual effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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Images
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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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a modified nickel cobalt lithium manganate positive electrode material and a preparation method thereof, belonging to the technical field of positive electrode materials. The preparation method comprises the following steps: mixing the modified mixed solution with a nickel cobalt lithium manganate matrix to be coated for reaction, and freeze-drying; the modified mixed solution is obtained by mixing modified chitosan coating solution and silane coupling agent modified conductive particles; the modified chitosan coating solution is obtained by mixing modified chitosan obtained by modifying chitosan with an imidazole compound having carboxyl with a solvent, and the silane coupling agent is silane having ethoxy. The method can effectively improve the binding force between the modified chitosan and the matrix; in the freeze drying process, the solvent in the modified chitosan coating liquid firstly forms an ice crystal structure, and then is directly sublimated and volatilized to be removed, so that a hole structure is left, the hole structure of the nickel cobalt lithium manganate matrix is improved, the migration and diffusion of lithium ions are facilitated, and the multiplying power and the cycle performance of corresponding materials can be improved.
Description
Technical Field
The invention relates to the technical field of positive electrode materials, in particular to a modified nickel cobalt lithium manganate positive electrode material and a preparation method thereof.
Background
The lithium nickel cobalt manganese oxide positive electrode material currently faces the problems of fast cycle capacity attenuation, agglomerated particle pulverization, poor structural stability and the like under a high voltage condition, and in order to alleviate the problems, a metal oxide, a fluoride, a phosphate, a silicate and a carbon material are generally adopted for coating in the prior art.
Although the existing coating mode can relieve the problems of agglomerated particle pulverization and poor structural stability under the high voltage condition to a certain extent, the improvement of the material cycle retention rate is still needed to be further improved.
In view of this, the invention is particularly proposed.
Disclosure of Invention
One of the objectives of the present invention is to provide a method for preparing a modified lithium nickel cobalt manganese oxide positive electrode material to solve the above technical problems.
The second purpose of the invention is to provide a modified coated nickel cobalt lithium manganate positive electrode material prepared by the preparation method.
The application can be realized as follows:
in a first aspect, the application provides a preparation method of a modified nickel cobalt lithium manganate positive electrode material, which comprises the following steps: mixing the modified mixed solution with a lithium nickel cobalt manganese oxide matrix to be coated for reaction so as to form a modified chitosan film on the surface of the lithium nickel cobalt manganese oxide matrix, and then carrying out freeze drying so as to enable the modified chitosan film to form a porous structure;
the modified mixed solution is obtained by mixing modified chitosan coating solution and silane coupling agent modified conductive particles; the modified chitosan coating solution is obtained by mixing modified chitosan and a solvent; the modified chitosan is obtained by modifying chitosan with imidazole compound with carboxyl; the silane coupling agent is a silane having an ethoxy group.
In an alternative embodiment, the modified mixture is sprayed onto the surface of the lithium nickel cobalt manganate substrate to be coated, followed by freeze-drying.
In an alternative embodiment, the mass ratio of the modified chitosan coating liquid to the silane coupling agent modified conductive particles to the nickel cobalt lithium manganate matrix is 80-100.
In an alternative embodiment, the modified chitosan coating solution contains 30-50g of modified chitosan per liter.
In an alternative embodiment, the solvent is an aqueous acetic acid solution.
In an alternative embodiment, the concentration of acetic acid in the aqueous acetic acid solution is 0.5 to 1.5% by volume.
In an alternative embodiment, the modified chitosan is obtained by acylation reaction of an imidazole compound having a carboxyl group with chitosan.
In an alternative embodiment, the imidazole compound having a carboxyl group includes at least one of imidazole-4-acetic acid and imidazole-1-carboxylic acid.
In an alternative embodiment, the molar ratio of imidazole compound having carboxyl groups to chitosan is from 1 to 3:2-5.
In an alternative embodiment, the mesh number of the chitosan is 40-80 mesh and the degree of deacetylation of the chitosan is 85-95%.
In an alternative embodiment, the silane coupling agent is an epoxy silane having an ethoxy group.
In an alternative embodiment, the silane coupling agent is a cycloaliphatic epoxy silane having an ethoxy group.
In an alternative embodiment, the epoxysilane is triethoxy [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl ] silane.
In an alternative embodiment, the conductive particles include at least one of zinc oxide and carbon nanotubes.
In an alternative embodiment, the lithium nickel cobalt manganese oxide substrate is formed by mixing and sintering a nickel cobalt manganese precursor and a lithium source.
In an alternative embodiment, the nickel cobalt manganese precursor is a nickel cobalt manganese hydroxide.
In an alternative embodiment, the lithium source comprises lithium carbonate.
In an alternative embodiment, the preparing of the lithium nickel cobalt manganese oxide substrate further comprises: and crushing the sintered material to obtain the nickel-cobalt lithium manganate powder.
In an optional embodiment, the lithium nickel cobalt manganese oxide powder has a median particle size of 10 to 20 μm.
In an alternative embodiment, the freeze-drying is vacuum drying in a freezing environment.
In an alternative embodiment, the method further comprises: and (3) washing the nickel cobalt lithium manganate matrix coated with the porous modified chitosan film on the surface to remove residual solvent, then carrying out solid-liquid separation, and drying the solid phase.
In a second aspect, the application provides a modified lithium nickel cobalt manganese oxide cathode material prepared by the preparation method of any one of the preceding embodiments.
The beneficial effect of this application includes:
the carboxyl on the imidazole compound reacts with the active amino of the chitosan to form chemical bonding, so that the modified chitosan solution with the imidazole structure is obtained, and the dissolution of transition metal in the cycle process of the anode material can be effectively inhibited.
By using the silane coupling agent group with the ethoxy group, on one hand, intermolecular acting force can be formed between the silane coupling agent group and hydroxyl groups and amino groups which are not reacted on the chitosan (namely, good bonding force is formed between the positions of the film), and on the other hand, the silane coupling agent group also has good bonding force with the substrate, so that the bonding force between the modified chitosan and the nickel cobalt lithium manganate substrate and between the internal structures of the film are improved.
The porous modified chitosan film contains conductive particles, so that the conductivity of the positive electrode material can be improved.
After freeze drying, the modified chitosan film forms a porous structure, which is beneficial to the migration and diffusion of lithium ions, and further can improve the multiplying power and the cycle performance of corresponding materials.
The correspondingly prepared modified nickel cobalt lithium manganate positive electrode material has good cycle retention rate and rate capability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
Fig. 1 is an SEM image of a modified lithium nickel cobalt manganese oxide positive electrode material prepared in example 1 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The modified lithium nickel cobalt manganese oxide positive electrode material and the preparation method thereof provided by the application are specifically described below.
The application provides a preparation method of a modified nickel cobalt lithium manganate positive electrode material, which comprises the following steps: and mixing the modified mixed solution with the nickel cobalt lithium manganate matrix to be coated for reaction so as to form a modified chitosan film on the surface of the nickel cobalt lithium manganate matrix, and then freeze-drying so as to enable the modified chitosan film to form a porous structure.
The modified mixed solution is obtained by mixing modified chitosan coating solution and silane coupling agent modified conductive particles; the modified chitosan coating solution is obtained by mixing modified chitosan and a solvent; the modified chitosan is obtained by modifying chitosan with imidazole compound with carboxyl; the silane coupling agent is a silane having an ethoxy group.
The modified chitosan is obtained by acylation reaction of imidazole compound with carboxyl and chitosan. Specifically, carboxyl on the imidazole compound reacts with active amino of chitosan to form chemical bonding, so that a modified chitosan solution with an imidazole structure is obtained. The modified chitosan solution can effectively inhibit the dissolution of transition metal of the anode material in the circulation process.
Preferably, the imidazole compound having a carboxyl group used herein preferably includes at least one of imidazole-4-acetic acid and imidazole-1-carboxylic acid. Compared with other imidazole compounds with carboxyl, the two compounds can obtain the cathode material with higher cycle retention rate under the preparation conditions of the application.
In the preparation process, the molar ratio of the imidazole compound having carboxyl groups to the chitosan is 1-3:2-5, and can be, for example, 1:2, 1:3, 1:4, 1:5, 2:2, 2:3, 2:4, 2:5, 3:2, 3:4 or 3:5, and the like, and can also be any other value within the range of 1-3:2-5.
It is to be noted that the chitosan used has a mesh number of 40-80 mesh and a degree of deacetylation of 85-95% to ensure high solubility of the chitosan.
In the application, each liter of the modified chitosan coating solution contains 30-50g (such as 30g, 35g, 40g, 45g or 50 g) of modified chitosan.
The solvent used in the modified chitosan coating solution is acetic acid aqueous solution, and the volume concentration of acetic acid in the acetic acid aqueous solution is 0.5-1.5%, so that the modified chitosan with an imidazole structure can be fully dissolved.
The silane coupling agent used in the application has the ethoxy group, on one hand, the silane coupling agent can form intermolecular acting force with unreacted hydroxyl and amino on chitosan (namely, the silane coupling agent can enable the positions of the film to have good bonding force), and on the other hand, the silane coupling agent can also have good bonding force with the substrate, so that the bonding force between the modified chitosan and the nickel cobalt lithium manganate substrate and between the internal structures of the film can be improved. The porous modified chitosan film contains conductive particles, so that the conductivity of the positive electrode material can be improved.
Preferably, the silane coupling agent is an epoxy silane having an ethoxy group. More preferably, the silane coupling agent is an alicyclic epoxy silane having an ethoxy group.
In some embodiments, the epoxysilane is triethoxy [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl ] silane. The molecular structure of the substance contains three hydrolyzable alkoxy (ethoxy), and the dual reactivity enables the substance to improve the combination and compatibility degree between the nickel cobalt lithium manganate matrix and the modified chitosan through the bidirectional chemical reaction between the substance and the nickel cobalt lithium manganate matrix.
In other embodiments, other cycloaliphatic epoxysilane species having ethoxy groups may also be employed.
The conductive particles may include at least one of zinc oxide and carbon nanotubes, by way of example. Further, it may be conductive graphite, conductive carbon black, graphene, carbon fiber, or the like.
The use of the conductive particles can improve the conductivity of the positive electrode material.
The preparation method of the silane coupling agent modified conductive particles can be that the conductive particles are added into an organic solvent (such as toluene) for ultrasonic dispersion to obtain a suspension, then the silane coupling agent is added for ultrasonic dispersion, the mixture reacts for 3 to 6 hours at a constant temperature of between 80 and 90 ℃, and the silane coupling agent modified conductive particles are obtained by centrifugal separation at normal temperature.
Wherein, the mass ratio of the silane coupling agent to the conductive particles can be 3-5:8-10, wherein the dosage of the organic solvent and the conductive particles is 20-30mL:0.8-1g.
In the present application, the modified chitosan coating solution and the nickel cobalt lithium manganate matrix may have a mass ratio of 80 to 100.
If the amount of the modified chitosan coating solution or the silane coupling agent modified conductive particles is too small, the bonding force between the substrate and the modified chitosan film is poor. If the amount of the modified chitosan coating solution is too large, or the amount of the silane coupling agent modified conductive particles is too large, the excessive attachment on the surface of the nickel-cobalt lithium manganate substrate is easy to influence the performance of the substrate such as the reduction of lithium ion deintercalation capability.
For example, the nickel cobalt lithium manganate matrix can be prepared by mixing and sintering a nickel cobalt manganese precursor and a lithium source.
The nickel-cobalt-manganese precursor can be nickel-cobalt-manganese hydroxide, and the lithium source can be lithium carbonate or lithium hydroxide.
Further, the preparation of the nickel cobalt lithium manganate matrix further comprises the following steps: and crushing the sintered material to obtain the nickel-cobalt lithium manganate powder.
Preferably, the median particle diameter of the crushed lithium nickel cobalt manganese oxide powder is 10-20 μm.
By using the nickel-cobalt lithium manganate powder with the particle size as a substrate, the particles can be prevented from agglomerating, and the nickel-cobalt lithium manganate powder can be uniformly and effectively coated by modified mixed liquid.
It should be noted that the nickel cobalt lithium manganate substrate used in the present application is a common nickel cobalt lithium manganate precursor in the field, and the present application does not excessively limit the chemical formula, the preparation process and the preparation conditions thereof, and specifically refers to the related prior art.
In this application, the cladding of modified mixed liquid to nickel cobalt lithium manganate base member can be: and spraying the modified mixed solution on the surface of each lithium nickel cobalt manganese oxide substrate to be coated, and then mixing the substrates sprayed with the modified mixed solution.
In the above process, the relationship between the amount of the modified mixed solution and the nickel cobalt lithium manganate matrix may be 83 to 105, such as 83.
The mixing of the above-mentioned respective matrices may be carried out at 50 to 60 ℃.
It should be noted that, the mixing process is performed at 50-60 ℃, so that the adhesion reaction rate of the modified mixed solution and the nickel cobalt lithium manganate matrix can be increased, and the coating binding force is tighter.
In the present application, freeze-drying is vacuum drying in a freezing environment, which may refer to related prior art and is not described herein in detail.
In the freeze drying process, the solvent in the modified chitosan coating liquid is firstly frozen into a solid state at a lower temperature, and then the water in the solvent is directly sublimated into a gas state without passing through a liquid state under vacuum, so that the material is dehydrated and dried. After sublimation, the position corresponding to the moisture in the original solid state forms a hole structure, and meanwhile, the process can also remove the moisture possibly existing on the surface or inside of the precursor, so that the pore structure of the nickel cobalt lithium manganate matrix is improved, the migration and diffusion of lithium ions are facilitated, and the multiplying power and the cycle performance of corresponding materials can be improved.
Further, after freeze drying, the nickel cobalt lithium manganate matrix coated with the porous modified chitosan film on the surface is washed to remove residual solvent, and then solid-liquid separation is carried out, and the solid phase is dried.
Correspondingly, the application also provides a modified nickel cobalt lithium manganate positive electrode material which is prepared by the preparation method.
The modified nickel cobalt lithium manganate positive electrode material can relieve volume strain in a circulation process, inhibit surface side reaction and improve electronic conductivity, and has high coulombic efficiency, circulation stability and rate capability.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a modified lithium nickel cobalt manganese oxide cathode material, which is prepared in the following manner:
step (1): spraying the modified mixed solution on a nickel cobalt lithium manganate matrix (LiNi) according to the proportion of 105g 0.9 Co 0.05 Mn 0.05 O 2 Median particle diameter of 15 μm).
The modified mixture is obtained by mixing modified chitosan coating liquid and silane coupling agent modified conductive particles.
The modified chitosan coating solution is prepared by mixing modified chitosan and 1vt% acetic acid aqueous solution according to the proportion of 30g.
The silane coupling agent modified conductive particles are prepared by the following method: adding zinc oxide into toluene, performing ultrasonic dispersion to obtain suspension, adding triethoxy [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl ] silane, performing ultrasonic dispersion, reacting at constant temperature of 85 ℃ for 5 hours, and performing centrifugal separation at normal temperature to obtain the silane coupling agent modified conductive particles. Wherein the mass ratio of the triethoxy [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl ] silane to the zinc oxide is 3:8, the dosage of the toluene and the zinc oxide is 25mL:1g of the total weight of the composition.
The mass ratio of the modified chitosan coating liquid to the silane coupling agent modified conductive particles to the nickel cobalt lithium manganate matrix is 100.
Step (2): and mixing and reacting the nickel cobalt lithium manganate matrix attached with the modified mixed solution at 60 ℃ to form a modified chitosan film on the surface of the nickel cobalt lithium manganate matrix, and then cooling to room temperature.
And (3): and (3) freeze-drying the material obtained in the step (2) to enable the modified chitosan membrane to form a porous structure.
And (4): and (3) washing the dried product with water to remove residual acetic acid, and drying the water to obtain the modified nickel cobalt lithium manganate cathode material.
Example 2
The present example differs from example 1 in that: imidazole-1-carboxylic acid is used instead of imidazole-4-acetic acid.
Example 3
This example differs from example 1 in that: each liter of the modified chitosan coating solution contains 40g of modified chitosan.
Example 4
This example differs from example 1 in that: each liter of the modified chitosan coating solution contains 50g of modified chitosan.
Example 5
This example differs from example 1 in that: the mass ratio of the modified chitosan coating liquid to the silane coupling agent modified conductive particles to the nickel cobalt lithium manganate matrix is 80.
Example 6
This example differs from example 1 in that: the mass ratio of the modified chitosan coating liquid to the silane coupling agent modified conductive particles to the nickel cobalt lithium manganate matrix is (90).
Example 7
This example differs from example 1 in that: the molar ratio of imidazole-4-acetic acid to chitosan is 1:2.
Example 8
This example differs from example 1 in that: the molar ratio of imidazole-4-acetic acid to chitosan is 3:5.
Comparative example 1
This comparative example differs from example 1 in that: the modified mixture is obtained by mixing chitosan coating liquid and silane coupling agent modified conductive particles. Wherein the chitosan coating solution is prepared by dissolving unmodified chitosan in an acetic acid aqueous solution.
That is, in this comparative example, chitosan was not modified with an imidazole compound having a carboxyl group.
Comparative example 2
This comparative example differs from example 1 in that: the modified mixed solution does not contain modified chitosan, and only contains conductive particles modified by a silane coupling agent.
Comparative example 3
This comparative example differs from example 1 in that: the modified mixed solution is obtained by mixing the modified chitosan coating solution and the conductive particles, and does not contain a silane coupling agent.
That is, the conductive particles in this comparative example were not modified with a silane coupling agent.
Comparative example 4
This comparative example differs from example 1 in that: the modified mixed solution is obtained by mixing modified chitosan coating solution and silane coupling agent, and does not contain conductive particles.
Comparative example 5
The comparative example differs from example 1 in that:
the imidazole compound is:
Comparative example 6
This comparative example differs from example 1 in that: the imidazole compound having a carboxyl group is imidazole-4,5-dicarboxylic acid.
Comparative example 7
This comparative example differs from example 1 in that: the silane coupling agent is gamma-methacryloxypropyl trimethoxy.
Comparative example 8
This comparative example differs from example 1 in that: the silane coupling agent is 2- (3,4-epoxycyclohexylalkyl) ethyltrimethoxysilane with the molecular formula of C 11 H 22 O 4 Si。
Comparative example 9
This comparative example differs from example 1 in that: silane coupling agent ethoxy trimethylsilane, molecular formula is C 5 H 14 OSi。
Test examples
(1) Taking the cathode material prepared in example 1 as an example, scanning is performed on the cathode material by an electron microscope, and an SEM image of the cathode material is shown in fig. 1.
(2) The cathode materials obtained in the examples 1 to 8 and the comparative examples 1 to 9 are respectively prepared into button cells to be tested for the electrochemical performance of the lithium ion battery according to the following modes:
the method comprises the following steps of uniformly mixing a positive electrode active material, acetylene black and PVDF according to the mass ratio of 9.2 to 0.5, taking N-methylpyrrolidone as a solvent, coating the mixture on an aluminum foil, carrying out forced air drying at 80 ℃ for 8 hours, and carrying out vacuum drying at 120 ℃ for 12 hours. The cell was assembled in an argon-protected glove box with a negative electrode of lithium metal sheet, a separator of polypropylene film, and an electrolyte of 1M LiPF6-EC/DMC (1, V/V), and assembled into a button cell using a 2032 type button cell case in an argon-protected glove box, and then subjected to electrochemical performance tests at 25 ℃ of 3.0-4.5V, the results of which are shown in Table 1 below.
TABLE 1 test results
As can be seen from table 1: the modified nickel cobalt lithium manganate positive electrode material prepared by the preparation method provided by the application has a good cycle retention rate.
In conclusion, the scheme provided by the application can effectively improve the binding force between the modified chitosan and the matrix; in the freeze drying process, the solvent in the modified chitosan coating liquid firstly forms an ice crystal structure, and then is directly sublimated and volatilized to be removed, so that a hole structure is left, the hole structure of the nickel cobalt lithium manganate matrix is improved, the migration and diffusion of lithium ions are facilitated, and the multiplying power and the cycle performance of corresponding materials can be improved.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the modified nickel cobalt lithium manganate positive electrode material is characterized by comprising the following steps: mixing the modified mixed solution with a nickel cobalt lithium manganate matrix to be coated for reaction so as to form a modified chitosan film on the surface of the nickel cobalt lithium manganate matrix, and then freeze-drying so as to enable the modified chitosan film to form a porous structure;
the modified mixed solution is obtained by mixing modified chitosan coating solution and silane coupling agent modified conductive particles; the modified chitosan coating solution is obtained by mixing modified chitosan and a solvent; the modified chitosan is obtained by modifying chitosan with an imidazole compound with carboxyl; the silane coupling agent is a silane having an ethoxy group.
2. The preparation method according to claim 1, characterized in that the modified mixed solution is sprayed on the surface of the nickel cobalt lithium manganate matrix to be coated, and then is freeze-dried;
preferably, the mass ratio of the modified chitosan coating liquid to the silane coupling agent modified conductive particles to the nickel cobalt lithium manganate matrix is 80-100.
3. The method according to claim 1, wherein said modified chitosan coating solution comprises 30-50g of said modified chitosan per liter;
preferably, the solvent is an aqueous acetic acid solution;
preferably, the volume concentration of the acetic acid in the acetic acid aqueous solution is 0.5-1.5%.
4. The preparation method according to claim 3, wherein the modified chitosan is obtained by acylation reaction of an imidazole compound having a carboxyl group with chitosan;
preferably, the imidazole compound having a carboxyl group includes at least one of imidazole-4-acetic acid and imidazole-1-carboxylic acid;
preferably, the molar ratio of the imidazole compound having a carboxyl group to the chitosan is 1-3:2-5;
preferably, the mesh number of the chitosan is 40-80 mesh, and the deacetylation degree of the chitosan is 85-95%.
5. The production method according to claim 1, wherein the silane coupling agent is an epoxy silane having an ethoxy group;
preferably, the silane coupling agent is a cycloaliphatic epoxy silane having an ethoxy group;
more preferably, the epoxysilane is triethoxy [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl ] silane.
6. The production method according to claim 1, wherein the conductive particles include at least one of zinc oxide and carbon nanotubes.
7. The preparation method of claim 1, wherein the lithium nickel cobalt manganese oxide substrate is prepared by mixing and sintering a nickel cobalt manganese precursor and a lithium source;
preferably, the nickel-cobalt-manganese precursor is nickel-cobalt-manganese hydroxide;
preferably, the lithium source comprises lithium carbonate;
preferably, the preparation of the nickel cobalt lithium manganate matrix further comprises the following steps: crushing the sintered material to obtain nickel cobalt lithium manganate powder;
preferably, the median particle diameter of the lithium nickel cobalt manganese oxide powder is 10-20 μm.
8. The method of claim 1, wherein the freeze-drying is vacuum-drying in a freezing environment.
9. The method of claim 1, further comprising: and washing the nickel cobalt lithium manganate matrix coated with the porous modified chitosan film on the surface to remove residual solvent, then carrying out solid-liquid separation, and drying the solid phase.
10. A modified nickel cobalt lithium manganate positive electrode material, characterized by being prepared by the preparation method of any one of claims 1 to 9.
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