CN117229525B - Coating material of lithium ion battery anode material, and preparation method and application thereof - Google Patents
Coating material of lithium ion battery anode material, and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 72
- 239000011248 coating agent Substances 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 239000010405 anode material Substances 0.000 title claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 claims abstract description 18
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 17
- 239000013099 nickel-based metal-organic framework Substances 0.000 claims abstract description 15
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 238000009396 hybridization Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000007790 solid phase Substances 0.000 claims description 29
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 10
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 10
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000011247 coating layer Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000009777 vacuum freeze-drying Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- 239000010406 cathode material Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 7
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000004108 freeze drying Methods 0.000 description 6
- 239000012066 reaction slurry Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000010280 constant potential charging Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910012529 LiNi0.4Co0.3Mn0.3O2 Inorganic materials 0.000 description 3
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium ion battery materials, and discloses a coating material of a lithium ion battery anode material, a preparation method and application thereof. The coating material is a composite material Ni/Co-MOFs/COF prepared by hybridization of a Covalent Organic Framework (COF) and a Metal Organic Framework (MOF) of nickel and cobalt. Uniformly coating a layer of Ni/Co-MOFs/COF material on the surface of a lithium ion battery anode material matrix, wherein the coated Ni/Co-MOFs/COF material plays a role in protecting and stabilizing the anode material, inhibits side reaction between the anode material and electrolyte and prevents the anode material from collapsing in structure; the stability of the positive electrode material is improved, the dissolution of electrolyte to metal ions is prevented, and the rate capability and the cycle performance of the battery are improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a coating material of a lithium ion battery anode material, a preparation method and application thereof.
Background
Ternary cathode material LiNi of lithium ion battery x Co y Mn 1-x-y O 2 Has higher theoretical capacity, lower cost, higher safety, higher working voltage and higher environmental friendliness, and has extremely high commercial application value. The specific capacity of the ternary cathode material of the lithium ion battery increases along with the increase of the Ni content, but the mixed discharge effect of Ni in the Li layer is more obvious along with the increase of the Ni content, so that the cycle performance and the rate performance of the ternary cathode material are poor.
Surface coating is an important way for improving the cycle performance and the rate performance of ternary cathode materials, and common surface coating materials are oxides, carbon, fast ion conductors, phosphates and the like. Wherein, the oxide coating reduces the contact between the positive electrode material and the electrolyte, relieves the corrosion of the electrolyte to the positive electrode active material, but reduces the conductivity of the material; carbon coating can improve the conductivity and the rate capability of the anode material, but can reduce the tap density of the material; the fast ion conductor coating can improve the rate performance of the positive electrode material, but the increase of the coating thickness can inhibit electron transfer during charge/discharge; the phosphate coating can improve the ion transmission performance of the positive electrode material, prevent the surface of the positive electrode material from directly contacting with the electrolyte, and inhibit side reaction and formation of a resistive surface film. The search for better coating means to modify the positive electrode material has been the key research direction in the industry.
Disclosure of Invention
The first object of the invention is to provide a coating material of a positive electrode material of a lithium ion battery and a preparation method thereof.
The second object of the invention is to provide a lithium ion battery anode material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following specific technical solutions.
Firstly, the invention provides a preparation method of a coating material of a lithium ion battery anode material, which comprises the following steps:
step (1), adding a nickel source, a cobalt source and 2-amino terephthalic acid (H) into N, N-Dimethylformamide (DMF) 2 BDC-NH 2 ) Then adding ethanol and deionized water, stirring, and reacting; after the reaction is finished, solid-liquid separation, washing and vacuum cooling are carried outLyophilizing the solid phase to obtain an intermediate material;
step (2), mixing the intermediate material with 1, 4-phenylenediamine, trimellitic aldehyde, dimethyl sulfoxide and deionized water for reaction; after the reaction is finished, filtering, washing and drying the solid phase to obtain the composite material Ni/Co-MOFs/COF.
In a further preferred embodiment, in the step (1), the ratio of the addition amounts of the N, N-dimethylformamide, the nickel source, the cobalt source and the 2-aminoterephthalic acid is as follows: (30-40 ml) 1mmol:1mmol (0.1-0.5 mmol).
In a further preferred scheme, the volume ratio of the N, N-dimethylformamide to the ethanol to the deionized water is (2-6): 1:1.
in a further preferred embodiment, in step (1), the reaction conditions include at least: the reaction temperature is 100-150 ℃. Further preferably, the reaction time is 8 to 12 hours.
In a further preferred embodiment, in the step (1), the nickel source is at least one of nickel sulfate, nickel nitrate, nickel chloride and nickel acetate.
In a further preferred embodiment, in the step (1), the cobalt source is at least one of cobalt sulfate, cobalt nitrate, cobalt chloride and cobalt acetate.
In a further preferred embodiment, in step (1), the washing conditions include at least: ethanol is used for washing, and deionized water is used for washing.
In a further preferred scheme, in the step (2), the relation of the addition amounts of the intermediate material, the 1, 4-phenylenediamine, the trimellitic aldehyde, the dimethyl sulfoxide and the deionized water is as follows: 0.5g (0.5-2 g) (40-55 ml) (10-20 ml).
In a further preferred embodiment, in step (2), the reaction conditions include at least: the reaction temperature is 150-180 ℃. Further preferably, the reaction time is 6 to 12 hours.
In a further preferred embodiment, in step (2), the washing conditions include at least: the washing reagent is ethanol.
In a further preferred embodiment, in step (2), the drying conditions include at least: and (5) drying at room temperature.
Secondly, the invention provides a coating material of a lithium ion battery anode material, wherein the coating material is a composite material Ni/Co-MOFs/COF prepared by hybridization of a Covalent Organic Framework (COF) and Metal Organic Frameworks (MOFs) of nickel and cobalt, and the coating material is prepared by the method.
In addition, the invention provides a lithium ion battery anode material, which comprises a matrix material and a coating layer; the molecular formula of the matrix material is LiNi x Co y Mn 1-x-y O 2 Wherein 0 is<x<1，0<y<1, and x+y<1, a step of; the coating layer is a composite material Ni/Co-MOFs/COF prepared by hybridization of a Covalent Organic Framework (COF) and Metal Organic Frameworks (MOFs) of nickel and cobalt.
Based on the same inventive concept, the invention provides a preparation method of the lithium ion battery anode material, which comprises the following steps:
and uniformly mixing the Ni/Co-MOFs/COF of the composite material with the matrix material, and sintering in a non-oxidizing atmosphere to obtain the composite material.
In a further preferred scheme, the mass ratio relationship between the Ni/Co-MOFs/COF of the composite material and the matrix material is 1-5: 100.
in a further preferred embodiment, the non-oxidizing atmosphere is an inert gas atmosphere.
In a further preferred embodiment, the sintering conditions include at least: the temperature rising rate is 1-10 ℃/min. Further preferably, the sintering temperature is 400 to 650 ℃. Further preferably, the sintering time is 5 to 20 hours.
MOFs provide good channels for lithium ion conduction due to their structural adjustability, porous structure, and surface functionality. The Covalent Organic Framework (COF) is a two-dimensional or three-dimensional framework material with regular pore channels or holes formed by covalent bonding of organic units, has the advantages of large specific surface area, adjustable function, good stability, low density and the like, is beneficial to providing a good lithium ion conduction channel and improving the durability of a lithium ion battery. However, MOF and COF materials also have certain drawbacks, such as MOF being unstable in aqueous solutions and the structure being prone to collapse; COF has no metal node, has simpler function and needs to be further improved in catalytic performance. And the construction of the MOF-COF hybrid mesoporous material can improve the weaknesses of the MOF-COF hybrid mesoporous material, so that the electrochemical performance of the anode material is improved.
In addition, single metal MOF materials often suffer from poor structural stability, limiting their application. For example, ni-MOFs typically exhibit high capacitance characteristics during electrocatalysis, whereas Co-MOFs exhibit low capacitance, but cycle stable characteristics. Compared with a single metal MOF material, the coexistence of the bimetallic ions shows a synergistic effect, and can promote the delocalization of electrons in the framework, so that the electron conductivity of the material is improved. Ni/Co-MOFs materials can increase capacity and enhance cycle stability.
The invention has the following obvious beneficial effects:
the method for preparing the composite Ni/Co-MOFs/COF is simple and easy to operate, has controllable process and can be popularized in large scale.
Uniformly coating a layer of Ni/Co-MOFs/COF material on the surface of a lithium ion battery anode material matrix, wherein the coated Ni/Co-MOFs/COF material plays a role in protecting and stabilizing the anode material, inhibits side reaction between the anode material and electrolyte and prevents the anode material from collapsing in structure; the stability of the positive electrode material is improved, the dissolution of electrolyte to metal ions is prevented, and the rate capability and the cycle performance of the battery are improved.
Drawings
Fig. 1 is an SEM image of the coating material prepared in example 1.
Fig. 2 is an SEM image of the coating-modified cathode material prepared in example 1.
Fig. 3 is a cycle curve of the positive electrode material assembled battery obtained in example 1 and comparative examples 1 to 4.
Fig. 4 is a cycle curve of a battery assembled with positive electrode materials before and after coating.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
(1) To 35ml of DMF were added 1mmol of nickel nitrate, 1mmol of cobalt nitrate and 0.25 mmol of 2-amino terephthalic acid (H 2 BDC-NH 2 ) Then 10 mL ethanol and 10 mL deionized water are added, and stirring is continued to obtain a mixed material. The resulting mixture was transferred to a 100 ml teflon reactor and heated at 120 ℃ for 12h. After solid-liquid separation of the reaction slurry, washing the solid phase with ethanol and then deionized water, and freeze-drying the solid phase under vacuum to obtain the precursor material.
(2) After mixing 0.5g of the precursor material in step (1) with 1g of 1, 4-phenylenediamine, 1g trimellitic aldehyde, 55ml dimethyl sulfoxide and 15 ml deionized water, the mixture was transferred to a high-pressure reaction kettle for sealing, and the mixture was heated in an oven at 150 ℃ for 12h. And then filtered to obtain a solid phase. The solid phase was washed with ethanol and dried at room temperature to obtain a coating material.
(3) Mixing 1g of the coating material obtained in the step (2) with 100g of LiNi 0.8 Co 0.1 Mn 0.1 O 2 And after uniformly mixing the anode materials, placing the anode materials in an atmosphere furnace for primary heat treatment, heating to 500 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, keeping the temperature at 5 h, naturally cooling to room temperature after finishing, and then crushing and sieving to obtain the coated modified anode materials.
Fig. 1 is an SEM image of a clad material, from which it can be seen that the clad material has a regular cubic structure.
Fig. 2 is an SEM image of the coating-modified cathode material, from which it can be seen that the particle surface of the cathode material is rough, the coating layer is present, and the coating layer is uniform.
Comparative example 1
Comparative example 1 differs from example 1 in that: and (3) no nickel nitrate is added in the step (1).
(1) To 35ml of DMF were added 1mmol of cobalt nitrate and 0.25 mmol of 2-amino terephthalic acid (H 2 BDC-NH 2 ) Then 10 mL ethanol and 10 mL deionized water are added, and stirring is continued to obtain a mixed material. The resulting mixture was transferred to a 100 ml teflon reactor and heated at 120 ℃ for 12h. After solid-liquid separation of the reaction slurry, washing the solid phase with ethanol and then deionized water, and freeze-drying the solid phase under vacuum to obtain the precursor material.
(2) After mixing 0.5g of the precursor material in step (1) with 1g of 1, 4-phenylenediamine, 1g trimellitic aldehyde, 55ml dimethyl sulfoxide and 15 ml deionized water, the mixture was transferred to a high-pressure reaction kettle for sealing, and the mixture was heated in an oven at 150 ℃ for 12h. And then filtered to obtain a solid phase. The solid phase was washed with ethanol and dried at room temperature to obtain a coating material.
(3) Mixing 1g of the coating material obtained in the step (2) with 100g of LiNi 0.8 Co 0.1 Mn 0.1 O 2 And after uniformly mixing the anode materials, placing the anode materials in an atmosphere furnace for primary heat treatment, heating to 500 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, keeping the temperature at 5 h, naturally cooling to room temperature after finishing, and then crushing and sieving to obtain the coated modified anode materials.
Comparative example 2
Comparative example 2 differs from example 1 in that: cobalt nitrate is not added in the step (1).
(1) To 35ml of DMF were added 1mmol of nickel nitrate and 0.25 mmol of 2-aminoterephthalic acid (H 2 BDC-NH 2 ) Then 10 mL ethanol and 10 mL deionized water are added, and stirring is continued to obtain a mixed material. The resulting mixture was transferred to a 100 ml teflon reactor and heated at 120 ℃ for 12h. After solid-liquid separation of the reaction slurry, washing the solid phase with ethanol and then deionized water, and freeze-drying the solid phase under vacuum to obtain the precursor material.
(2) After mixing 0.5g of the precursor material in step (1) with 1g of 1, 4-phenylenediamine, 1g trimellitic aldehyde, 55ml dimethyl sulfoxide and 15 ml deionized water, the mixture was transferred to a high-pressure reaction kettle for sealing, and the mixture was heated in an oven at 150 ℃ for 12h. And then filtered to obtain a solid phase. The solid phase was washed with ethanol and dried at room temperature to obtain a coating material.
(3) Mixing 1g of the coating material obtained in the step (2) with 100g of LiNi 0.8 Co 0.1 Mn 0.1 O 2 And after uniformly mixing the anode materials, placing the anode materials in an atmosphere furnace for primary heat treatment, heating to 500 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, keeping the temperature at 5 h, naturally cooling to room temperature after finishing, and then crushing and sieving to obtain the coated modified anode materials.
Comparative example 3
Comparative example 3 differs from example 1 in that: ni/Co-MOFs materials were synthesized.
The specific implementation process is as follows:
to 35ml of DMF were added 1mmol of nickel nitrate, 1mmol of cobalt nitrate and 0.25 mmol of terephthalic acid (H 2 BDC), then 10 mL ethanol and 10 mL deionized water were added, and stirring was continued to obtain a mixed material. The resulting mixture was transferred to a 100 ml teflon reactor and heated at 120 ℃ for 12h. After solid-liquid separation of the reaction slurry, washing the solid phase with ethanol and then deionized water, and freeze-drying the solid phase under vacuum to obtain the Ni/Co-MOFs material.
Comparative example 4
Comparative example 4 differs from example 1 in that: COF materials were synthesized.
The specific implementation process is as follows:
1g of 1, 4-phenylenediamine, 1g trimellitic aldehyde, 55ml dimethyl sulfoxide and 15 ml deionized water are mixed, transferred into a high-pressure reaction kettle for sealing, and heated in an oven at 150 ℃ for 12h. And then filtered to obtain a solid phase. Washing the solid phase with ethanol, and drying the solid phase at room temperature to obtain the COF material.
Example 2
(1) To 30 ml of DMF were added 1mmol of nickel nitrate, 1mmol of cobalt nitrate and 0.1 mmol of 2-aminoterephthalic acid (H 2 BDC-NH 2 ) However, it isAnd then adding 5mL ethanol and 5mL deionized water, and continuously stirring to obtain a mixed material. The resulting mixture was transferred to a 100 ml teflon reactor and heated at 100 ℃ for 10 h. After solid-liquid separation of the reaction slurry, washing the solid phase with ethanol and then deionized water, and freeze-drying the solid phase under vacuum to obtain the precursor material.
(2) After mixing 0.5g of the precursor material in step (1) with 0.5g of 1, 4-phenylenediamine, 0.5. 0.5g trimellitic aldehyde, 40. 40ml dimethyl sulfoxide and 10. 10 ml deionized water, the mixture was transferred to an autoclave for sealing, and heated in an oven at 180 ℃ for 6. 6 h. And then filtered to obtain a solid phase. The solid phase was washed with ethanol and dried at room temperature to obtain a coating material.
(3) Mixing 5g of the coating material obtained in the step (2) with 100g of LiNi 0.6 Co 0.2 Mn 0.2 O 2 And after uniformly mixing the anode materials, placing the anode materials in an atmosphere furnace for primary heat treatment, heating to 400 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, keeping the temperature at 20h, naturally cooling to room temperature after finishing, and then crushing and sieving to obtain the coated modified anode materials.
Example 3
(1) To 40ml of DMF were added 1mmol of nickel nitrate, 1mmol of cobalt nitrate and 0.5mmol of 2-amino terephthalic acid (H 2 BDC-NH 2 ) Then, 20mL of ethanol and 20mL of deionized water were added thereto, and stirring was continued to obtain a mixed material. The resulting mixture was transferred to a 100 ml teflon reactor and heated at 150 ℃ for 8 h. After solid-liquid separation of the reaction slurry, washing the solid phase with ethanol and deionized water for multiple times, and freeze-drying the solid phase under vacuum to obtain the precursor material.
(2) After mixing 0.5g of the precursor material in step (1) with 2g of 1, 4-phenylenediamine, 2g trimellitic aldehyde, 55ml dimethyl sulfoxide and 20ml deionized water, transferring to a high-pressure reaction kettle for sealing, and heating 12h in an oven at 150 ℃. And then filtered to obtain a solid phase. The solid phase was washed with ethanol and dried at room temperature to obtain a coating material.
(3) Mixing 3g of the coating material obtained in the step (2) with 100g of LiNi 0.4 Co 0.3 Mn 0.3 O 2 And after uniformly mixing the anode materials, placing the anode materials in an atmosphere furnace for primary heat treatment, heating to 650 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, keeping the temperature at 10 h, naturally cooling to room temperature after finishing, and then crushing and sieving the crushed anode materials to obtain the coated modified anode materials.
Coating modified cathode materials obtained in example 1-example 3, comparative example 1-comparative example 4 and LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 0.6 Co 0.2 Mn 0.2 O 2 、LiNi 0.4 Co 0.3 Mn 0.3 O 2 The battery is assembled by: mixing a positive electrode material, a binder PVDF and a conductive agent according to the proportion of 8:1:1, dry-grinding for 10min, adding a solvent NMP, uniformly stirring by using a homogenizer to prepare positive electrode slurry, and uniformly coating the positive electrode slurry on an aluminum foil; taking a metal lithium sheet as a negative electrode; lithium ion secondary electrolyte LB-037 (1M LiPF6 in DEC:EC:EMC =1:1:1 vol%) was used as electrolyte and Celgard2325 as separator to assemble the lithium ion secondary electrolyte into a button cell of LIR 2032.
The electrical properties of the cells were tested: in a constant temperature box at 25 ℃, constant current charging is carried out to a voltage of 4.3V at a rate of 0.1C, constant voltage charging is carried out to a voltage of 0.01C, the constant voltage charging is carried out, then 0.1C is used for discharging to 3V, circulation is carried out twice, then the battery is charged to a voltage of 4.3V at a rate of 0.5C, constant voltage charging is carried out to a voltage of 0.05C, the constant voltage charging is carried out, then 0.5C is used for discharging to 3V, and the charge and discharge capacity is recorded.
Fig. 3 and 4 show the test results. As can be seen from the figure, the battery assembled from the positive electrode material of comparative example 1 exhibited higher capacity than the battery assembled from comparative example 2, whereas the battery assembled from the positive electrode material of comparative example 2 had better stability than the battery assembled from the positive electrode material of comparative example 1. The cathode materials of comparative example 3 and comparative example 4 were respectively assembled with low capacity and poor cycle stability. The battery assembled with the positive electrode material of example 1 has a high capacity and excellent cycle stability.
In addition, liNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 0.6 Co 0.2 Mn 0.2 O 2 、LiNi 0.4 Co 0.3 Mn 0.3 O 2 Assembled batteryThe capacity retention after 50 cycles was 68.55%, 71.90% and 76.41%, respectively. According to the technical scheme provided by the invention, the capacity retention rates of the coating modified cathode material after 50 circles of circulation are 84.89%, 85.45% and 83.55%, respectively. Obviously, the coating modification method provided by the invention can obviously improve the capacity of the anode material and the cycle performance of the anode material.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the coating material of the lithium ion battery anode material is characterized by comprising the following steps of:
step (1), adding a nickel source, a cobalt source and 2-amino terephthalic acid (H) into N, N-Dimethylformamide (DMF) 2 BDC-NH 2 ) Adding ethanol and deionized water, stirring, and reacting; after the reaction is finished, solid-liquid separation, washing and vacuum freeze-drying of the solid phase to obtain an intermediate material; the proportional relation of the addition amounts of the N, N-dimethylformamide, the nickel source, the cobalt source and the 2-amino terephthalic acid is as follows: (30-40 ml) 1mmol:1mmol (0.1-0.5 mmol);
step (2), mixing the intermediate material with 1, 4-phenylenediamine, trimellitic aldehyde, dimethyl sulfoxide and deionized water for reaction; after the reaction is finished, filtering, washing and drying the solid phase to obtain the composite material Ni/Co-MOFs/COF.
2. The preparation method of claim 1, wherein the volume ratio of the N, N-dimethylformamide, the ethanol and the deionized water is (2-6): 1:1.
3. the preparation method according to claim 1 or 2, wherein in the step (1), the temperature of the reaction is 100 to 150 ℃; the reaction time is 8-12 h.
4. The method of claim 1, wherein in the step (2), the relationship among the amounts of the intermediate material, 1, 4-phenylenediamine, trimellitic aldehyde, dimethyl sulfoxide and deionized water is: 0.5g (0.5-2 g) (40-55 ml) (10-20 ml).
5. The method according to claim 1 or 4, wherein in the step (2), the temperature of the reaction is 150 to 180 ℃; the reaction time is 6-12 hours.
6. The coating material of the lithium ion battery anode material is characterized in that the coating material is a composite material Ni/Co-MOFs/COF prepared by hybridization of a covalent organic framework and metal organic frameworks of nickel and cobalt, and is prepared by the preparation method of any one of claims 1-5.
7. The lithium ion battery anode material is characterized by comprising a matrix material and a coating layer; the molecular formula of the matrix material is LiNi x Co y Mn 1-x-y O 2 Wherein 0 is<x<1，0 <y<1, and x+y<1, a step of; the coating layer is the coating material according to claim 6.
8. The method for preparing a positive electrode material for a lithium ion battery according to claim 7, comprising the steps of:
the coating material according to claim 6, wherein the coating material and the base material are uniformly mixed and sintered in a non-oxidizing atmosphere.
9. The method for preparing the lithium ion battery anode material according to claim 8, wherein the mass ratio relationship between the coating material and the matrix material is 1-5: 100.
10. the method for preparing the positive electrode material of the lithium ion battery according to claim 8 or 9, wherein the temperature rising rate of sintering is 1-10 ℃/min; the sintering temperature is 400-650 ℃.
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