CN111755665B - Lithium ion battery negative electrode material, battery negative electrode and application thereof - Google Patents
Lithium ion battery negative electrode material, battery negative electrode and application thereof Download PDFInfo
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- CN111755665B CN111755665B CN201910234745.7A CN201910234745A CN111755665B CN 111755665 B CN111755665 B CN 111755665B CN 201910234745 A CN201910234745 A CN 201910234745A CN 111755665 B CN111755665 B CN 111755665B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 82
- 239000007773 negative electrode material Substances 0.000 title description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 239000003575 carbonaceous material Substances 0.000 claims description 26
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 22
- 239000002033 PVDF binder Substances 0.000 claims description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- 239000006258 conductive agent Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- -1 350G Chemical compound 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 239000004584 polyacrylic acid Substances 0.000 claims description 5
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 5
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- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 125000005580 triphenylene group Chemical group 0.000 claims description 5
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- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
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- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 abstract description 10
- 239000006182 cathode active material Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 5
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011268 mixed slurry Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910020489 SiO3 Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PKRGYJHUXHCUCN-UHFFFAOYSA-N cyclohexanehexone Chemical compound O=C1C(=O)C(=O)C(=O)C(=O)C1=O PKRGYJHUXHCUCN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- SKBJSCXKLGRIPF-UHFFFAOYSA-N triphenylene-1,2,3,4,5,6-hexamine Chemical group NC1=C(N)C(N)=C2C3=C(N)C(N)=CC=C3C3=CC=CC=C3C2=C1N SKBJSCXKLGRIPF-UHFFFAOYSA-N 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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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- General Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a lithium ion battery cathode material, a lithium ion battery and application thereof. The lithium ion battery cathode active material enables the prepared lithium ion battery to have high specific capacity, high rate performance, high cycle stability, high energy density and high power density.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a lithium ion battery cathode material, a battery cathode and application thereof.
Background
In recent years, consumer electronics, electric vehicles, and electrical energy storage systems have been rapidly developed. These devices are increasingly demanding on energy storage devices. At present, lithium ion batteries are mainstream energy storage devices in the market, but with the continuous improvement of the performance requirements of various electronic and electric equipment on energy storage devices, the performance of the lithium ion batteries is in the forefront. Currently, how to improve the energy density and cycle life of a lithium ion battery is a problem to be solved urgently in the field of energy storage. The most effective method is to develop novel lithium ion battery anode and cathode materialsAnd (5) feeding. At present, the most widely used lithium ion battery negative electrode material is graphite, but the specific capacity of the graphite is lower (the theoretical specific capacity is 372.07 mAh.g)-1) The requirement of high energy density of the lithium ion battery cannot be met. In order to increase the energy density of the lithium ion battery, silicon is used for the negative active material. The theoretical specific capacity of silicon as a negative active material is up to 4209.7 mAh.g-1However, the silicon negative electrode has a very serious swelling problem during the operation of the battery, so that the cycle life of the battery is very short, and thus the silicon negative electrode cannot be well used for a lithium ion battery. In order to solve the problem of silicon expansion, graphite and silicon are often doped at present to improve the stability of the battery, but the introduction of graphite can reduce the specific capacity of the negative electrode material. At present, the specific capacity of commercial silicon negative electrode materials applied in large scale is less than 600 mAh.g-1. Therefore, the development of a novel negative active material is one of effective solutions for improving the energy density and cycle life of a lithium ion battery.
CN106531980A discloses a lithium ion battery cathode material and a preparation method and application thereof, wherein in the preparation, silicon powder and a dispersing agent are subjected to wet ball milling to obtain silicon slurry; uniformly mixing the silicon slurry with graphite and a conductive agent, and then carrying out spray drying to obtain spheroidal particles; mechanically fusing the spheroidal particles to obtain a precursor A; mixing the precursor A and resin VC, then carrying out mechanical fusion, and then coating in a coating kettle to obtain a precursor B; mixing the precursor B and the pitch VC, then carrying out mechanical fusion, and then coating in a coating kettle to obtain a precursor C; sintering, carbonizing and screening the precursor C in an inert atmosphere to obtain the lithium ion battery cathode material.
CN107195884A discloses a lithium ion battery cathode material, in particular to a lithium metasilicate doped graphene lithium ion battery cathode material, which is prepared by the following steps: adding the mixture of silicon powder and graphite oxide into an ethanol aqueous solution containing lithium hydroxide, and synthesizing Li by adopting a hydrothermal method2SiO3A GE precursor; li2SiO3And sintering the/GE precursor under the protection of argon to obtain the lithium metasilicate doped graphene lithium ion battery cathode material.
CN105655560A discloses a preparation method of a silicon-doped graphene lithium ion battery negative electrode material: firstly, uniformly mixing graphene powder and silicon source powder in a weight ratio of 1:10-1000: 1; secondly, placing the mixture obtained in the first step into a reaction furnace, heating to 1000-1600 ℃, keeping introducing protective gas, keeping the temperature for 1-120min after the temperature reaches a set temperature; and thirdly, cooling to obtain the silicon-doped graphene lithium ion battery cathode material.
Although the lithium ion battery cathode material related to the prior art can improve the energy density and the cycle life of the lithium ion battery to a certain extent, the effect is limited, so that the development of a novel lithium ion battery cathode active material which can obviously improve the specific capacity, the energy density, the rate capability and the cycle stability of the battery cathode has very important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a lithium ion battery negative electrode material, a battery negative electrode and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the invention provides a lithium ion battery cathode material, which comprises a nitrogen-containing two-dimensional conjugated carbon material formed by connecting a triphenylene unit and a cyclohexyl unit through a pyrazine ring, and the structure of the material is shown as formula I:
wherein the dashed lines indicate that the structure shown in formula I extends infinitely in a two-dimensional plane.
The nitrogen-containing two-dimensional conjugated carbon material is formed by connecting a triphenylene unit and a cyclohexyl unit through a pyrazine ring, and simultaneously has a regular and ordered two-dimensional structure, a conjugated large-pi structure, a uniform microporous structure and a nitrogen-doped carbon structure. It possesses a lamellar structure similar to graphite, which allows lithium ions to intercalate well; and the porous structure has a shape and size controllable, an ideal channel is provided for the diffusion of lithium ions and electrolyte, the utilization rate of the material can be improved, and the specific capacity is further improved. In addition, nitrogen atoms are introduced into the two-dimensional conjugated carbon material, so that additional lithium ion binding sites can be provided, and the specific capacity of the battery negative electrode is further improved.
Preferably, the nitrogen-containing two-dimensional conjugated carbon material has a nanoscale lamellar structure.
Preferably, the thickness of the nitrogen-containing two-dimensional conjugated carbon material is 0.7 to 1nm, for example, 0.7nm, 0.75nm, 0.8nm, 0.84nm, 0.86nm, 0.9nm, 1nm or the like, preferably 0.8 to 0.9 nm. This is a single-sheet layer structure, not a multi-sheet layer structure.
The thickness of the nitrogen-containing two-dimensional conjugated carbon material is specially selected within the range of 0.7-1nm, because the lamellar structure with the thickness within the range can expose more electrochemical active sites, so that more lithium ions can be combined and more electrolyte can be contacted, and the capacity of the material is improved.
In another aspect, the present invention provides a lithium ion battery negative electrode comprising a conductive agent, a binder, and the nitrogen-containing two-dimensional conjugated carbon material described above.
Preferably, the nitrogen-containing two-dimensional conjugated carbon material accounts for 50-99% of the lithium ion battery negative electrode by mass, such as 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 88%, 90%, 95%, 98%, or 99%, preferably 80-98%.
Preferably, the conductive agent includes any one of acetylene black, 350G, carbon fiber, carbon nanotube, ketjen black, conductive graphite, or graphene, or a combination of at least two thereof, such as a combination of acetylene black and carbon fiber, a combination of conductive graphite and graphene, a combination of carbon fiber and carbon nanotube, and ketjen black, and the like.
Preferably, the conductive agent includes any one of carbon black, acetylene black, carbon nanotubes, or conductive graphite, or a combination of at least two thereof.
Preferably, the conductive agent accounts for 0.5-30% of the lithium ion battery negative electrode by mass, such as 0.5%, 1%, 2%, 5%, 10%, 15%, 18%, 20%, 25% or 30%, and preferably 5-15%.
Preferably, the binder includes any one of polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethylcellulose, polyvinylidene fluoride, polyacrylic acid, sodium alginate and polyimide or a combination of at least two thereof, such as a combination of polyvinyl alcohol and polytetrafluoroethylene, a combination of sodium carboxymethylcellulose and polyvinylidene fluoride, a combination of polyacrylic acid and sodium alginate and polyimide, and the like.
Preferably, the binder comprises any one of or a combination of at least two of sodium carboxymethylcellulose, polyvinylidene fluoride, or polyacrylic acid.
Preferably, the binder accounts for 0.1-30% of the lithium ion battery negative electrode by mass, such as 0.1%, 1%, 2%, 5%, 6%, 10%, 15%, 18%, 20%, 25%, or 30%, and preferably 1-6%.
In yet another aspect, the present invention provides a lithium ion battery comprising a lithium ion battery negative electrode as described above.
Compared with the prior art, the invention has the following beneficial effects:
(1) the lithium ion battery cathode active material can greatly improve the electrochemical performance of the lithium ion battery, effectively improve the specific capacity of the cathode, reduce the series internal resistance and obviously improve the energy density of the lithium ion battery.
(2) The lithium ion battery negative active material related by the invention has high specific capacity. Under the charge/discharge rate of 0.5C, the specific discharge capacity is 670mAh g-1The above.
(3) The lithium ion battery cathode active material has good rate capability. Under the condition of 10C charging/discharging rate, its specific discharge capacity still can be up to 475mAh g-1。
(4) The lithium ion battery cathode active material has good cycle stability. Under the condition of 10C charge/discharge rate, after 10000 cycles of charge and discharge, the capacity retention rate is still higher than 80%.
Drawings
FIG. 1 is a charge-discharge specific capacity curve of a battery prepared in example 1 at a current density of 0.5C;
FIG. 2 is a charge-discharge specific capacity curve of the battery prepared in example 1 at a current density of 1C;
FIG. 3 is a charge-discharge specific capacity curve at a current density of 2C for the battery prepared in example 1;
FIG. 4 is a charge-discharge specific capacity curve at a current density of 5C for the battery prepared in example 1;
FIG. 5 is a charge-discharge specific capacity curve at a current density of 10C for the battery prepared in example 1;
FIG. 6 is a curve of specific charge-discharge capacity at current densities of 0.5C, 1C, 2C, 5C and 10C for the battery prepared in example 6;
FIG. 7 is a graph showing the change in specific discharge capacity with the number of cycles of the battery obtained in example 1;
FIG. 8 is a graph of the change in specific discharge capacity with cycle number for the battery made in example 6;
fig. 9 is a graph showing the change in specific discharge capacity at 10C charge/discharge rate of the battery prepared in example 1;
fig. 10 is a graph showing the change in specific discharge capacity at 10C charge/discharge rate of the battery prepared in example 2;
fig. 11 is a graph showing the change in specific discharge capacity at 10C charge/discharge rate of the battery obtained in example 6.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The test equipment used in the following examples was a blue cell test system.
Example 1
The present embodiment provides a lithium ion battery negative electrode material, which includes a nitrogen-containing two-dimensional conjugated carbon material formed by connecting a triphenylene unit and a cyclohexyl unit through a pyrazine ring, and has a structure shown in the following formula:
the thickness of the material was 0.84 nm.
The material is prepared by a process referred to in another patent (201710847482.8) of the applicant: the precursor of the nitrogenous two-dimensional conjugated carbon material is prepared by condensation reaction of Hexaaminotriphenylene (HATP) and hexaketocyclohexane, and is prepared by steps of heat treatment, stripping and the like.
Then, preparing a lithium ion battery negative pole piece by using the material:
212.8mg of a two-dimensional conjugated carbon material (80%), 39.9mg of carbon black (15%) and 13.3mg of polyvinylidene fluoride (PVDF) (5%) were mixed, ground into powder, and then an appropriate amount of N-methylpyrrolidone (NMP) was added to make the mixture into a uniformly mixed slurry; the prepared slurry was coated on a clean aluminum foil with a glass rod to prepare a film of 25mm thickness. The film is dried in vacuum at 70 ℃ overnight and then cut into sheets with the diameter of 11mm to obtain the negative pole piece of the lithium ion battery.
Further preparation of assembled button half-cells:
a metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm is used as a negative electrode, the prepared negative electrode active material-containing pole piece is used as a positive electrode, a 1, 3-dioxolane and glycol dimethyl ether mixed solution (v/v is 1:1) containing 1.0M LiTFSI is used as an electrolyte, and the 2325 type button half cell is assembled.
Example 2
In this embodiment, the lithium ion battery negative electrode material prepared in example 1 is used to prepare a lithium ion battery negative electrode sheet:
212.8mg of a two-dimensional conjugated carbon material (80%), 39.9mg of carbon black (15%) and 13.3mg of polyvinylidene fluoride (PVDF) (5%) were mixed, ground into powder, and then an appropriate amount of N-methylpyrrolidone (NMP) was added to make the mixture into a uniformly mixed slurry; the prepared slurry was coated on a clean aluminum foil with a glass rod to prepare a film of 25mm thickness. The film is dried in vacuum at 70 ℃ overnight and then cut into sheets with the diameter of 22mm to obtain the negative pole piece of the lithium ion battery.
Further preparation of assembled button half-cells:
a metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm is used as a negative electrode, the prepared negative electrode active material-containing pole piece is used as a positive electrode, a 1, 3-dioxolane and glycol dimethyl ether mixed solution (v/v is 1:1) containing 1.0M LiTFSI is used as an electrolyte, and the 2325 type button half cell is assembled.
Example 3
In this embodiment, the lithium ion battery negative electrode material prepared in example 1 is used to prepare a lithium ion battery negative electrode sheet:
212.8mg of a two-dimensional conjugated carbon material (80%), 39.9mg of conductive graphite (15%) and 13.3mg of polyvinylidene fluoride (PVDF) (5%) were mixed, ground into powder, and then an appropriate amount of NMP was added to prepare a uniformly mixed slurry from the mixture; the prepared slurry was coated on a clean aluminum foil with a glass rod to prepare a film of 25mm thickness. The film is dried in vacuum at 70 ℃ overnight and then cut into sheets with the diameter of 22mm to obtain the negative pole piece of the lithium ion battery.
Further preparation of assembled button half-cells:
a metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm is used as a negative electrode, the prepared negative electrode active material-containing pole piece is used as a positive electrode, a 1, 3-dioxolane and glycol dimethyl ether mixed solution (v/v is 1:1) containing 1.0M LiTFSI is used as an electrolyte, and the 2325 type button half cell is assembled.
Example 4
In this embodiment, the lithium ion battery negative electrode material prepared in example 1 is used to prepare a lithium ion battery negative electrode sheet:
239.4mg of a two-dimensional conjugated carbon material (90%), 13.3mg of conductive graphite (5%) and 13.3mg of polyvinylidene fluoride (PVDF) (5%) were mixed, ground into powder, and then an appropriate amount of NMP was added to make the mixture into a uniformly mixed slurry; the prepared slurry was coated on a clean aluminum foil with a glass rod to prepare a film of 25mm thickness. The film is dried in vacuum at 70 ℃ overnight and then cut into sheets with the diameter of 11mm to obtain the negative pole piece of the lithium ion battery.
Further preparation of assembled button half-cells:
a metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm is used as a negative electrode, the prepared negative electrode active material-containing pole piece is used as a positive electrode, a 1, 3-dioxolane and glycol dimethyl ether mixed solution (v/v is 1:1) containing 1.0M LiTFSI is used as an electrolyte, and the 2325 type button half cell is assembled.
Example 5
In this embodiment, the lithium ion battery negative electrode material prepared in example 1 is used to prepare a lithium ion battery negative electrode sheet:
244.7mg of a two-dimensional conjugated carbon material (90%), 10.6mg of ketjen black (5%) and 10.6mg of polyvinylidene fluoride (PVDF) (5%) were mixed, ground into powder, and then an appropriate amount of NMP was added to make the mixture into a uniformly mixed slurry; the prepared slurry was coated on a clean aluminum foil with a glass rod to prepare a film of 25mm thickness. The film is dried in vacuum at 70 ℃ overnight and then cut into sheets with the diameter of 11mm to obtain the negative pole piece of the lithium ion battery.
Further preparation of assembled button half-cells:
a metal lithium sheet with the diameter of 16mm and the thickness of 0.5mm is used as a negative electrode, the prepared negative electrode active material-containing pole piece is used as a positive electrode, a 1, 3-dioxolane and glycol dimethyl ether mixed solution (v/v is 1:1) containing 1.0M LiTFSI is used as an electrolyte, and the 2325 type button half cell is assembled.
Example 6
The present embodiment provides a lithium ion battery negative electrode material, which includes a nitrogen-containing two-dimensional conjugated carbon material formed by connecting a triphenylene unit and a cyclohexyl unit through a pyrazine ring, and has a structure shown in the following formula:
the thickness of the material is 30nm, and the material is not in a single-sheet layer structure but in a multi-sheet layer structure.
The material is prepared by a process referred to in another patent (201710847482.8) of the applicant.
Then, the material is used for preparing the lithium ion battery negative pole piece, and the method is the same as the example 1.
Assembled button half-cells were further prepared in the same manner as in example 1.
Electrochemical properties (specific capacity, rate capability and cycling stability) of the assembled button half-cells prepared in example 1, example 2 and example 6 were tested as follows:
test 1: the assembled button half-cell prepared in example 1 was tested for specific charge and discharge capacity at different current densities, and the test results are shown in fig. 1-5 (fig. 1, 2, 3, 4, and 5 are specific charge and discharge capacity curves at current densities of 0.5C, 1C, 2C, 5C, and 10C, respectively). As can be seen from fig. 1 to 5: the lithium ion battery negative active material can greatly improve the charge-discharge specific capacity and the rate capability of the lithium ion battery, and the discharge specific capacity is 670 mAh.g under the current density of 0.5C-1The above; under the current density of 10C, the specific discharge capacity still reaches 475 mAh.g-1。
The assembled button half-cell prepared in example 6 was tested for specific charge/discharge capacity at different current densities (0.5C, 1C, 2C, 5C, 10C), and the test results are shown in fig. 6, which shows that: the specific capacity of the material of the multi-layer structure in example 6 (the specific discharge capacity at 0.5C rate is less than 300mAh g)-1) Is far lower than the specific capacity of the single-layer structure material (under the multiplying power of 0.5C, the specific discharge capacity is 670 mAh.g)-1As described above), it is demonstrated that the thickness of the lithium ion battery negative electrode material according to the present invention (i.e., whether it has a monolithic layer structure) can significantly affect the electrochemical performance of the nitrogen-containing two-dimensional conjugated carbon material.
And (3) testing 2: the assembled button half cell prepared in example 1 was tested for its specific capacity change over cycle number to examine the rate capability of the cell, and the test results are shown in fig. 7. As can be seen from the figure: after charging for multiple circles at different multiplying powers, the specific capacity of the battery under the same multiplying power is not changed, which shows that the material has excellent multiplying power performance, namely, the power density of the battery is favorably improved.
The discharge specific capacity change chart of the assembled button half-cell prepared in example 6 along with the number of cycles was tested to examine the rate performance of the cell, and the test results are shown in fig. 8. As can be seen from the figure: the material with the multi-layer structure in example 6 has a low specific capacity, but the rate capability is excellent, which indicates that the nitrogen-containing two-dimensional conjugated structure provided in the present invention has excellent rate capability.
And (3) testing: the assembled button half cells prepared in examples 1 and 2 were subjected to charge/discharge cycling tests at 10C rate, as shown in fig. 9 and 10. As can be seen from fig. 9 (example 1): at 0.70mg cm-2The specific capacity of the material at 10C charge/discharge rate is higher than 500 mAh.g under the surface density-1(ii) a As can be seen from fig. 10 (example 2): at 1.53mg cm-2The specific capacity of the material is still higher than 400 mAh.g at the charging/discharging rate of 10C under higher surface density-1This indicates that the material is suitable for use in high loading and high rate batteries.
The assembled button half cells prepared in example 6 were subjected to charge/discharge cycling tests at 10C rate as shown in fig. 11. As can be seen from fig. 11: the nitrogen-containing two-dimensional conjugated carbon material with the multi-layer structure is low in specific capacity under the multiplying power of 10C, but the cycle performance is excellent, which shows that the nitrogen-containing two-dimensional conjugated structure provided by the invention has excellent electrochemical stability.
The applicant states that the present invention is illustrated by the above examples to provide a lithium ion battery negative electrode material, a lithium ion battery negative electrode and applications thereof, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention is necessarily implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (15)
1. The lithium ion battery negative electrode is characterized by comprising a conductive agent, a binder and a nitrogen-containing two-dimensional conjugated carbon material;
the nitrogen-containing two-dimensional conjugated carbon material is formed by connecting a triphenylene unit and a cyclohexyl unit through a pyrazine ring, and the structure of the nitrogen-containing two-dimensional conjugated carbon material is shown as a formula I:
wherein the dashed lines indicate that the structure shown in formula I extends infinitely in a two-dimensional plane.
2. The negative electrode for a lithium ion battery according to claim 1, wherein the nitrogen-containing two-dimensional conjugated carbon material has a nano-scale lamellar structure.
3. The negative electrode for lithium ion batteries according to claim 1, wherein the nitrogen-containing two-dimensional conjugated carbon material has a thickness of 0.7 to 1 nm.
4. The negative electrode for lithium ion batteries according to claim 1, wherein the nitrogen-containing two-dimensional conjugated carbon material has a thickness of 0.8 to 0.9 nm.
5. The negative electrode for a lithium ion battery according to claim 1, wherein the nitrogen-containing two-dimensional conjugated carbon material accounts for 50 to 99% by mass of the negative electrode for a battery.
6. The negative electrode for a lithium ion battery according to claim 1, wherein the nitrogen-containing two-dimensional conjugated carbon material accounts for 80 to 98% by mass of the negative electrode for a battery.
7. The lithium ion battery negative electrode of claim 1, wherein the conductive agent comprises any one of acetylene black, 350G, carbon fiber, carbon nanotube, ketjen black, conductive graphite, or graphene, or a combination of at least two thereof.
8. The lithium ion battery negative electrode of claim 1, wherein the conductive agent comprises any one of carbon black, acetylene black, carbon nanotubes, or conductive graphite, or a combination of at least two thereof.
9. The lithium ion battery negative electrode of claim 1, wherein the conductive agent is present in an amount of 0.5 to 30% by mass of the battery negative electrode.
10. The lithium ion battery negative electrode of claim 1, wherein the conductive agent is 5-15% by mass of the battery negative electrode.
11. The lithium ion battery negative electrode of claim 1, wherein the binder comprises any one of or a combination of at least two of polyvinyl alcohol, polytetrafluoroethylene, sodium carboxymethylcellulose, polyvinylidene fluoride, polyacrylic acid, sodium alginate, or polyimide.
12. The lithium ion battery negative electrode of claim 1, wherein the binder comprises any one of sodium carboxymethylcellulose, polyvinylidene fluoride, or polyacrylic acid, or a combination of at least two thereof.
13. The lithium ion battery negative electrode of claim 1, wherein the binder is present in an amount of 0.1 to 30% by mass of the battery negative electrode.
14. The lithium ion battery negative electrode of claim 1, wherein the binder is present in an amount of 1 to 6% by mass of the battery negative electrode.
15. A lithium ion battery comprising the lithium ion battery negative electrode of claim 1.
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