CN117276496A - High-energy-density quick-filling alloy graphite composite material and preparation method and application thereof - Google Patents
High-energy-density quick-filling alloy graphite composite material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 38
- 239000010439 graphite Substances 0.000 title claims abstract description 38
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 31
- 239000000956 alloy Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000011049 filling Methods 0.000 title claims description 4
- 239000000463 material Substances 0.000 claims abstract description 60
- 239000000571 coke Substances 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 23
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011733 molybdenum Substances 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 238000006722 reduction reaction Methods 0.000 claims abstract description 11
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 22
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 12
- 239000007773 negative electrode material Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000002006 petroleum coke Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920005546 furfural resin Polymers 0.000 claims description 4
- 238000005087 graphitization Methods 0.000 claims description 4
- 239000011331 needle coke Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000011311 coal-based needle coke Substances 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- 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
- 238000010000 carbonizing Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 14
- 239000006258 conductive agent Substances 0.000 description 14
- 239000011230 binding agent Substances 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- 239000010405 anode material Substances 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 Polyethylene Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of lithium ion battery materials, in particular to a high-energy density quick-charging alloy graphite composite material, a preparation method and application thereof, wherein the alloy graphite composite material is of a core-shell structure, the inner core is molybdenum doped porous graphite, the outer shell is graphene doped amorphous carbon, and the mass of the outer shell is 2-5wt% of that of the alloy graphite composite material. The invention uses MoS 2 The molybdenum doped porous coke precursor material is generated by the reduction reaction of the molybdenum doped porous coke precursor material and the coke, so that the channel of the material can be effectively improved, the high specific capacity of Mo and the conductivity thereof are utilized to improve the power performance, and simultaneously, amorphous carbon and graphene obtained by carbonizing resin on the outer layer are mixed and coated on the outer layer, so that the electron conduction of the material is improvedThe electrical property and the first efficiency, and the obtained material improves the ionic and electronic conductivity of the material and improves the multiplying power performance of the material by constructing the characteristics of the porous channel of the inner core and the electronic conductivity of the outer shell.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a high-energy density quick-charging alloy graphite composite material, a preparation method and application thereof.
Background
The current marketized negative electrode material mainly takes artificial graphite or natural graphite, the specific capacity of the negative electrode material reaches 355-360mAh/g, the specific capacity is close to 372mAh/g, and the negative electrode material is difficult to be greatly improved; while silicon-based materials have a high degree of crystallinitySpecific capacity (silicon monoxide, 1600 mAh/g), but has the limitation of high full electrical expansion, and silicon is a semiconductor material with electronic conductivity deviation and power performance deviation. Molybdenum disulfide (MoS) 2 ) Is a three-layer structure separated by Van der Waals force, and S-Mo-S is a layered structure formed by tightly stacking covalent bonds, has high electronic conductivity, and is MoS 2 As a lithium battery anode material, the specific capacity is 750mAh/g, the lithium battery anode material has good stability and strong lithium storage capacity, but the problem of slightly high full-charge expansion still exists, and the stress variation in the particles in the circulation process causes the cracking and pulverization of the particles, so that the circulation performance is reduced.
For example, patent application number CN201710329858.6 discloses a bamboo charcoal/molybdenum sulfide composite negative electrode material of a lithium ion battery and a preparation method thereof, and the bamboo charcoal/molybdenum sulfide composite material prepared by the invention is directly applied to the negative electrode material of the lithium ion battery, has good electrochemical performance, has a specific discharge capacity of 1100-1500 mAh/g at 0.01-3.0V, and maintains the specific discharge capacity of 650-810 mAh/g after 90 times of cyclic discharge, and has higher initial specific capacity but power performance deviation and cyclic performance deviation. Therefore, there is a need for a negative electrode material that can achieve both specific capacity and power and cycle properties.
Disclosure of Invention
In order to improve the specific capacity and the power performance of graphite, the invention improves the specific capacity and the power performance of the material by blending molybdenum sulfide in coke, and coats amorphous carbon on the outer layer of the material to improve the first efficiency and reduce the expansion.
The first aspect of the invention provides a high-energy density rapid-charging alloy graphite composite material, which is of a core-shell structure, wherein the inner core is molybdenum doped porous graphite, the outer shell is graphene doped amorphous carbon, and the mass of the outer shell is 2-5wt% of that of the alloy graphite composite material.
Further, the shell is composed of 5-20wt% graphene and 80-95wt% amorphous carbon.
The second aspect of the invention provides a method for preparing a high energy density rapid charging alloy graphite composite material, the method comprising the steps of:
s1, ball milling and blending a coke raw material, molybdenum disulfide and coke to obtain a precursor material, and further carrying out reduction reaction to obtain a molybdenum doped porous coke precursor material;
s2, mixing the molybdenum doped porous coke precursor material, the resin and the graphene, and then spray drying to obtain the alloy graphite composite material.
In some embodiments, the mass ratio of the coke-based feedstock, molybdenum disulfide, and coke is 1000: (100-200): (10-15).
The applicant finds in experiments that if the proportion of molybdenum disulfide is too large, the cycle performance is reduced, the proportion is too small, and the specific capacity amplitude of the lifting material is low; the coke reacts with molybdenum disulfide, C+MoS 2 ＝Mo+CS 2 The coke has low specific capacity and low first efficiency, mainly plays a role in reduction, and a small amount of coke and molybdenum disulfide generate metal Mo to improve the electronic conductivity of the material and generate holes after CS2 is volatilized, so that the liquid retention performance of the material is improved, and the cycle performance is improved.
In some embodiments, the reduction reaction is carried out at 800-1200 ℃ for 1-6 hours.
In some embodiments, the coke-based feedstock includes at least one of petroleum coke, needle coke, coal-based needle coke.
In some embodiments, the mass ratio of the molybdenum doped porous coke precursor material, resin, and graphene is 100: (10-20): (1-5).
In the system, if the addition amount of the resin is too large, the specific capacity and the compaction density can be reduced, and if the addition amount is too small, the quick-filling performance of the lifting material is limited; if the addition amount of the graphene is too large, the first efficiency and the compaction density of the graphene can be reduced, the addition amount of the graphene is too small, and the quick charging performance of the lifting material is limited.
In some embodiments, the resin comprises at least one of phenolic resin, furfural resin, epoxy resin, silicone resin, acrylic resin.
In some embodiments, the graphitization temperature is 2800 ℃ to 3200 ℃.
In some embodiments, the graphene is a solution of graphene in N-methylpyrrolidone at a concentration of 1-5wt%.
Further, the resin is chloroform solution of the resin, and the mass concentration is 1-10wt%.
The third aspect of the invention provides application of the alloy graphite composite material in preparing a lithium battery anode material.
Compared with the prior art, the invention has the following beneficial effects: the invention uses MoS 2 The molybdenum doped porous coke precursor material is generated by the reduction reaction of the molybdenum doped porous coke precursor material and the coke, so that a channel of the material can be effectively improved, the specific capacity and the conductivity of Mo per se are utilized to improve the power performance, meanwhile, amorphous carbon and graphene obtained by carbonizing resin on the outer layer are mixed and coated on the outer layer, the electronic conductivity and the first efficiency of the material are improved, and the ionic conductivity and the electronic conductivity of the material are improved by constructing the characteristics of the porous channel of the inner core and the electronic conductivity of the shell of the porous channel of the inner core, and the multiplying power performance of the material is improved.
Drawings
Fig. 1 is an SEM image of the high energy density rapid charging alloy graphite composite material prepared in example 1.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a high-energy density rapid-charging alloy graphite composite material, and the preparation method comprises the following steps:
s1, 1000g of petroleum coke and 150g of MoS 2 Adding 12g of coke into a ball mill, mixing for 24 hours according to the ball milling speed of 50rpm to obtain a precursor material, transferring the precursor material into a tube furnace, heating to 900 ℃ for reduction reaction for 3 hours to obtain a molybdenum-doped porous coke precursor material;
s2, adding 100g of molybdenum doped porous coke precursor material into 300g of chloroform solution of phenolic resin with the mass concentration of 5wt%, continuously adding 100g of N-methylpyrrolidone solution of graphene with the mass concentration of 3wt%, uniformly mixing, spray drying, and graphitizing at 3000 ℃ for 48 hours to obtain the alloy graphite composite material.
The phenolic resin was purchased from the Santa Clay, inc.
The petroleum coke is purchased from the Liaoning Jinzhou petrochemical company, inc.
Example 2
The embodiment provides a high-energy density rapid-charging alloy graphite composite material, and the preparation method comprises the following steps:
s1, 1000g of needle coke raw material and 100g of MoS 2 Adding 20g of coke into a ball mill, mixing for 72 hours according to the ball milling speed of 10rpm to obtain a precursor material, transferring the precursor material into a tube furnace, heating to 800 ℃ for reduction reaction for 6 hours to obtain a molybdenum doped porous coke precursor material;
s2, adding 100g of molybdenum doped porous coke precursor material into 100g of chloroform solution of furfural resin with the mass concentration of 1wt%, continuously adding 100g of graphene conductive agent with the mass concentration of 1wt%, uniformly mixing, spray drying, and graphitizing at 2800 ℃ for 72h to obtain the alloy graphite composite material.
The furfural resin was purchased from atactic holy spring group, inc.
The needle coke feedstock was purchased from Shandong allied New Material Limited.
Example 3
The embodiment provides a high-energy density rapid-charging alloy graphite composite material, and the preparation method comprises the following steps:
s1, 1000g of petroleum coke and 200g of MoS 2 Adding 15g of coke into a ball mill, mixing for 12 hours according to the ball milling speed of 100rpm to obtain a precursor material, transferring the precursor material into a tube furnace, heating to 1200 ℃ for reduction reaction for 1 hour to obtain a molybdenum doped porous coke precursor material;
s2, adding 100g of molybdenum doped porous coke precursor material into 200g of chloroform solution of epoxy resin with the mass concentration of 10wt%, continuously adding 100g of graphene conductive agent with the mass concentration of 5wt%, uniformly mixing, spray drying, and graphitizing at 3200 ℃ for 24h to obtain the alloy graphite composite material.
The epoxy resin was purchased from atactic holt spring group, inc.
Comparative example 1
This comparative example provides a high energy density rapid-alloyed graphite composite, the specific embodiment being the same as example 1, except that no MoS was added 2 And coke.
Comparative example 2
This comparative example provides a high energy density rapid alloyed graphite composite material, the specific embodiment being the same as example 1 except that no phenolic resin and no graphene are added.
Comparative example 3
This comparative example provides a high energy density rapid alloyed graphite composite material, the embodiment being the same as example 1 except 1000g Petroleum coke, 80g MoS 2 30g of coke.
Comparative example 4
The comparative example provides a high energy density rapid charging alloy graphite composite material, and the specific implementation mode is the same as example 1, except that 100g of molybdenum doped porous coke precursor material is added into 500g of chloroform solution with the mass concentration of 5wt% phenolic resin, 300g of graphene conductive agent with the mass concentration of 3wt% is continuously added and uniformly mixed.
Performance testing
(1) SEM test
SEM testing was performed on the high energy density rapid alloy graphite composite material prepared in example 1, and the results are shown in fig. 1. As can be seen from FIG. 1, the obtained composite material is granular, has a surface with a porous structure, and has a grain size of 5-10 μm.
(2) Button cell testing
The high energy density rapid charging alloy graphite composites prepared in examples 1-3 and the graphite composites of comparative examples 1-4 were assembled into button cells, respectively, as follows: to the negative electrode materialAdding binder, conductive agent and solvent, stirring and mixing to obtain negative electrode slurry, coating the negative electrode slurry on copper foil, oven drying, rolling, and cutting to obtain the final product. The binder is LA132 binder, the conductive agent is SP conductive agent, the solvent is secondary distilled water, and the weight ratio of the anode material, the SP conductive agent, the LA132 binder and the secondary distilled water is 95:1:4:220. The lithium metal sheet is used as a counter electrode, a Polyethylene (PE) film, a polypropylene (PP) film or a polyethylene propylene (PEP) composite film is used as a diaphragm, and LiPF is used 6 /EC+DEC(LiPF 6 The concentration of (2) was 1.2mol/L and the volume ratio of EC and DEC was 1:1) as an electrolyte, and the battery assembly was performed in an argon-filled glove box.
The prepared button cells are respectively arranged on a Wuhan blue electric CT2001A type cell tester, charge and discharge are carried out at a rate of 0.1C, the charge and discharge voltage ranges from 0.005V to 2.0V, and the first discharge capacity and the first discharge efficiency are measured. And the rate discharge capacity of 2C was measured to calculate rate performance (2C/0.1C).
Powder conductivity, powder OI value, graphitization degree and specific surface area of the negative electrode material are tested according to national standard GB/T-24533-2019 lithium ion battery graphite negative electrode material, and meanwhile, the diffusion coefficient of the material is tested through GITT, and the test result is shown in Table 1:
TABLE 1
As can be seen from table 1, the discharge capacity and the powder conductivity of the composite anode materials prepared in examples 1-3 are significantly higher than those of the comparative examples; the reason for this may be that the molybdenum sulfide doped with specific capacity in the embodiment in the material increases the specific capacity and the electronic conductivity of the material, and increases the rate capability and the specific capacity of the material for discharging. .
(3) Soft package battery test
The high energy density rapid charging alloy graphite composite materials prepared in examples 1 to 3 and comparative examples 1 to 4 were used as negative electrodes, respectively, and ternary materials (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) A positive electrode is prepared for the positive electrode material,by LiPF 6 (the solvent is EC+DEC, the volume ratio is 1:1, the concentration is 1.3 mol/L) is electrolyte, and Celebord 2400 is a diaphragm to prepare the 2Ah soft-package battery.
When the negative electrode is prepared, a binder, a conductive agent and a solvent are added into a negative electrode material, the materials are stirred and mixed uniformly to prepare negative electrode slurry, the negative electrode slurry is coated on a copper foil, and the negative electrode plate is prepared by drying, rolling and cutting. The binder is LA132 binder, the conductive agent is SP conductive agent, the solvent is secondary distilled water, and the weight ratio of the anode material, the SP conductive agent, the LA132 binder and the secondary distilled water is 95:1:4:220.
When the positive electrode is prepared, a binder, a conductive agent and a solvent are added into a positive electrode material, the mixture is stirred and mixed uniformly to prepare positive electrode slurry, the positive electrode slurry is coated on an aluminum foil, the aluminum foil is dried, rolled and cut to prepare a positive electrode plate, the binder is PVDF, the conductive agent is a carbon nano tube, and the solvent is N-methylpyrrolidone. The weight ratio of the positive electrode material, the conductive agent, the binder and the solvent is 93:3:4:180.
3.1 rate Performance test
The charge-discharge voltage ranges from 2.8V to 4.2V, the test temperature is 25+/-3.0 ℃, the charge is respectively carried out at 1.0C, 2.0C, 3.0C and 5.0C, the discharge is carried out at 1.0C, the constant current ratio of the battery in different charging modes is tested, and the results are shown in Table 2:
TABLE 2
As can be seen from Table 2, the rate charging performance of the battery pack of the invention is obviously better than that of the comparative example, and the charging time is shorter, so that the high-energy-density quick-charging alloy graphite composite material of the invention has good quick charging performance. The reason may be that the embodiment material has higher powder conductivity, reduces impedance and improves the constant current ratio of the material; by MoS 2 The molybdenum doped porous coke precursor material is generated by the reduction reaction of the molybdenum doped porous coke precursor material and the specific capacity and the conductivity of Mo per se are utilized to improve the power performance of the material channel; meanwhile, the embodiment has a larger diffusion coefficient, and the multiplying power performance of the material is improved.
3.2 cycle Performance test
The following experiments were performed on the flexible battery fabricated using the high energy density rapid charging alloy graphite composite materials of examples 1 to 3 and comparative examples 1 to 4: the capacity retention was measured at a charge/discharge rate of 1C/1C, a voltage range of 2.8-4.2V, and 500 charge/discharge cycles, and the results are shown in Table 3.
3.3 high temperature storage Performance test
Firstly, testing the discharge capacity QA of the battery in a state of being charged to 100%, then placing the battery in a constant temperature box at 55 ℃ for 30 days, then testing the residual capacity QB of the battery, then testing the capacity QC of the battery in a state of being charged to full charge, and then calculating the charge retention=QB/QA of the battery; capacity recovery = QC/QA, the results are shown in table 3.
TABLE 3 Table 3
As can be seen from table 3, the cycle performance of the lithium ion battery prepared from the high-energy density rapid-charging alloy graphite composite material prepared by the invention is superior to that of the comparative example, and the reason is probably that the amorphous carbon and graphene obtained by carbonizing the resin on the outer layer are mixed and coated on the outer layer, so that the structural stability of the material is improved, and the cycle performance is improved; meanwhile, the material of the embodiment has high graphitization degree, which is beneficial to the structural stability of the material, thereby improving the high-temperature storage performance.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The high-energy-density quick-filling alloy graphite composite material is characterized in that the alloy graphite composite material is of a core-shell structure, the inner core is molybdenum doped porous graphite, the outer shell is graphene doped amorphous carbon, and the mass of the outer shell is 2-5wt% of that of the alloy graphite composite material.
2. The method for preparing the alloy graphite composite material according to claim 1, wherein the preparation method comprises the following steps:
s1, ball milling and blending a coke raw material, molybdenum disulfide and coke to obtain a precursor material, and further carrying out reduction reaction to obtain a molybdenum doped porous coke precursor material;
s2, mixing the molybdenum doped porous coke precursor material, resin and graphene, and then spray drying, and graphitizing to obtain the alloy graphite composite material.
3. The preparation method according to claim 2, wherein the mass ratio of the coke raw material, molybdenum disulfide and coke is 1000: (100-200): (10-15).
4. The method according to claim 2, wherein the reduction reaction is carried out at 800 to 1200 ℃ for 1 to 6 hours.
5. The method according to claim 2, wherein the coke-based raw material comprises at least one of petroleum coke, needle coke, and coal-based needle coke.
6. The preparation method according to claim 2, wherein the mass ratio of the molybdenum doped porous coke precursor material, the resin and the graphene is 100: (10-20): (1-5).
7. The method of claim 6, wherein the resin comprises at least one of phenolic resin, furfural resin, epoxy resin, silicone resin, and acrylic resin.
8. The method of claim 7, wherein the graphitization temperature is 2800 ℃ to 3200 ℃.
9. The preparation method according to claim 2, wherein the graphene is an N-methylpyrrolidone solution of graphene, and the concentration is 1-5wt%.
10. The use of the alloy graphite composite material of claim 1 in the preparation of a negative electrode material for a lithium battery.
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