CN115974114A - Quick-filling graphite composite material and preparation method thereof - Google Patents
Quick-filling graphite composite material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 102
- 239000010439 graphite Substances 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000011049 filling Methods 0.000 title claims abstract description 16
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 38
- 239000007770 graphite material Substances 0.000 claims abstract description 21
- 229920001690 polydopamine Polymers 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 15
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 12
- 238000004070 electrodeposition Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 229960003638 dopamine Drugs 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims abstract description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000007773 negative electrode material Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 239000006258 conductive agent Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910021383 artificial graphite Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of lithium ion battery materials, and provides a quick-charging graphite composite material and a preparation method thereof, wherein the preparation method of the quick-charging graphite composite material comprises the following steps: s1, uniformly mixing graphite and sodium bicarbonate, introducing oxidizing gas for reaction, and then carrying out acid washing to obtain porous graphite; s2, taking a dopamine aqueous solution containing a solid electrolyte as a solution, taking porous graphite as a working electrode, taking a platinum electrode as a counter electrode, and performing electrochemical deposition by adopting a constant pressure method to obtain polydopamine-coated porous graphite; and S3, adding the polydopamine coated porous graphite into an organic solvent containing aluminum chloride, reacting for 1-6h at 60-120 ℃, filtering, drying and sintering to obtain the porous alumina/amorphous carbon coated graphite material. The quick-filling graphite composite material is prepared by the method. Through the technical scheme, the problems of low first-time efficiency and poor rate capability of the graphite material prepared in the prior art are solved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a quick-charging graphite composite material and a preparation method thereof.
Background
The existing marketable graphite surface coating material is amorphous carbon formed by carbonizing asphalt or resin so as to improve the first efficiency and the multiplying power of the graphite material. The main factors influencing the rate capability of the graphite material are as follows: the aggregate particle size of the material core, the electronic and ionic conductivity of the material surface coating material and the diffusion performance of the material surface. The superiority of the coating material has great influence on the electronic and ionic impedance and the diffusion coefficient of the material, the conventional graphite surface coating material is mainly amorphous carbon, and the improvement of the electronic conductivity of the material is not realized on the ionic conductivity of the material.
The invention patent application of application number 202110856231.2 discloses a graphite composite electrode material, which comprises an inner core, an intermediate layer and an outer layer, wherein the inner core is graphite, the intermediate layer is an inorganic lithium layer, and the outer layer is an organic lithium layer. Although the rate capability of the graphite composite electrode material is improved to a certain extent, the specific capacity of the material can be reduced due to the double-layer coating layer, and the preparation process is complex and difficult to industrialize.
Disclosure of Invention
The invention provides a quick-filling graphite composite material and a preparation method thereof, which solve the problems of low first efficiency and poor rate capability of a graphite material prepared in the prior art.
The technical scheme of the invention is as follows:
a preparation method of a quick-filling graphite composite material comprises the following steps:
s1, uniformly mixing graphite and sodium bicarbonate, introducing oxidizing gas for reaction, and then carrying out acid washing to obtain porous graphite;
s2, taking a dopamine aqueous solution containing a solid electrolyte as a solution, taking porous graphite as a working electrode, taking a platinum electrode as a counter electrode, and performing electrochemical deposition by adopting a constant pressure method to obtain polydopamine-coated porous graphite;
and S3, adding the polydopamine coated porous graphite into an organic solvent containing aluminum chloride, reacting for 1-6h at 60-120 ℃, filtering, drying and sintering to obtain the porous alumina/amorphous carbon coated graphite material.
According to a further technical scheme, in the S1, the mass ratio of graphite to sodium bicarbonate is 100.
In a further technical scheme, in the step S1, a mixing mode of the graphite and the sodium bicarbonate is ball milling.
As a further technical scheme, in the S1, the oxidizing gas is one of chlorine and sulfur dioxide, the flow rate of the oxidizing gas is 50-200mL/min, the reaction temperature is 200-300 ℃, and the reaction time is 30-300min.
As a further technical scheme, in the S2, the solid electrolyte Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 、Li 6.5 La 3 Zr 1.5 Nb 0.5 O 12 、Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 、Li 6 La 3 Zr 1.0 Ta 1.0 O 12 One or more of (a).
As a further technical scheme, in the step S2, the time of electrochemical deposition is 30-300min, and the voltage is 2V.
In the step S3, the mass concentration of aluminum chloride in the organic solvent containing aluminum chloride is 0.5% to 5%, and the organic solvent is one of ethanol, acetone, toluene, and dimethylformamide.
As a further technical scheme, in the step S3, the mass ratio of the aluminum chloride to the polydopamine-coated porous graphite material is 1-10.
As a further technical scheme, in the step S3, sintering is carried out in an inert gas atmosphere, the sintering temperature is 700-1200 ℃, and the sintering time is 1-6h.
The invention also provides a quick-filling graphite composite material which is prepared according to the preparation method of the quick-filling graphite composite material.
The working principle and the beneficial effects of the invention are as follows:
1. according to the invention, the polydopamine and the solid electrolyte are deposited in the pores of the porous graphite by an electrochemical deposition method, amorphous carbon with high density is filled in the pores of the porous graphite after the polydopamine is carbonized, so that the tap density and the cycle performance of the graphite composite material are improved, the prepared graphite composite material has a low powder OI value, the dynamic performance of the graphite composite material is improved, the lithium ion conductivity of the solid electrolyte is high, sufficient lithium ions are provided for the charge and discharge processes, the first efficiency and the rate capability of the graphite composite material as a negative electrode material are obviously improved under the synergistic effect of the amorphous carbon and the solid electrolyte, and the cycle performance of a battery taking the graphite composite material as the negative electrode material is improved.
2. According to the invention, the porous graphite of the core of the graphite composite material has a high specific surface area, so that the liquid absorption and retention capacity of the graphite composite material are improved, the cycle performance and the rate capability of a battery taking the graphite composite material as a negative electrode material are further improved, the porous alumina of the shell does not react with lithium ions in an electrolyte and consume lithium ions, the first efficiency of the graphite composite material as the negative electrode material is further improved, and the porous structure improves the dynamic performance of the graphite composite material.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is an SEM image of a porous alumina/amorphous carbon coated graphite material prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.
Example 1
A preparation method of a quick-filling graphite composite material comprises the following steps:
s1, adding 100g of artificial graphite and 5g of sodium bicarbonate into a ball mill, uniformly mixing, transferring into a tubular furnace, introducing chlorine gas, reacting at the gas flow rate of 100mL/min and the reaction temperature of 270 ℃ for 60min, soaking for 24h by using 0.1mol/L dilute hydrochloric acid, and washing with deionized water to obtain porous graphite;
s2, mixing 5g of Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 Adding the solution into 100mL of 0.1mol/L dopamine aqueous solution, uniformly dispersing the solution to serve as a solvent, pressing porous graphite into a blocky structure to serve as a working electrode, taking a platinum electrode as a counter electrode, performing electrochemical deposition for 60min by adopting a constant pressure method at the voltage of 2V, and then washing the electrode for 10 times by adopting 0.1mol/L dilute hydrochloric acid to obtain a polydopamine-coated porous graphite material;
and S3, adding 5g of aluminum chloride into 500g of ethanol to prepare an aluminum chloride solution with the mass concentration of 1%, then adding 100g of polydopamine-coated porous graphite material, then adding ammonia water to adjust the pH value to 7, reacting at 80 ℃ for 3 hours, filtering after the reaction is finished, vacuum-drying at 80 ℃ for 48 hours, and sintering at high temperature of 900 ℃ for 3 hours under the inert atmosphere of argon gas to obtain the porous alumina/amorphous carbon-coated graphite composite material.
Example 2
A preparation method of a quick-filling graphite composite material comprises the following steps:
s1, adding 100g of artificial graphite and 1g of sodium bicarbonate into a ball mill, uniformly mixing, transferring to a tubular furnace, introducing sulfur dioxide gas, reacting at the gas flow rate of 50mL/min and the reaction temperature of 200 ℃ for 300min, soaking for 10h by using 0.1mol/L dilute hydrochloric acid, and washing with deionized water to obtain porous graphite;
s2, mixing 1g of Li 6.5 La 3 Zr 1.5 Nb 0.5 O 12 Adding the solution into 500mL of 0.1mol/L dopamine aqueous solution, uniformly dispersing the solution to serve as a solvent, pressing porous graphite into a blocky structure to serve as a working electrode, using a platinum electrode as a counter electrode, performing electrochemical deposition for 30min by adopting a constant pressure method, wherein the voltage is 2V, and then washing for 10 times by adopting 0.1mol/L dilute hydrochloric acid to obtain a polydopamine-coated porous graphite material;
and S3, adding 1g of aluminum chloride into 200g of acetone to prepare an aluminum chloride solution with the mass concentration of 0.5%, then adding 100g of polydopamine-coated porous graphite material, then adding ammonia water to adjust the pH value to 7, reacting at 60 ℃ for 6 hours, filtering after the reaction is finished, vacuum-drying at 80 ℃ for 24 hours, and sintering at high temperature under an argon inert atmosphere, wherein the sintering temperature is 700 ℃ and the sintering time is 6 hours, so that the porous alumina/amorphous carbon-coated graphite composite material is obtained.
Example 3
A preparation method of a quick-filling graphite composite material comprises the following steps:
s1, adding 100g of artificial graphite and 10g of sodium bicarbonate into a ball mill, uniformly mixing, transferring into a tubular furnace, introducing chlorine gas, reacting at the gas flow rate of 50mL/min and the reaction temperature of 300 ℃ for 30min, soaking for 24 hours by using 0.1mol/L dilute hydrochloric acid, and washing with deionized water to obtain porous graphite;
s2, mixing 10g of Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 Adding into 500mL 0.1mol/L dopamine aqueous solution, dispersing uniformly to obtain solvent, pressing porous graphite into block structure and using as working electrode, using platinum electrode as counter electrode, performing electrochemical deposition by constant pressure method for 300min at 2V, and washing with 0.1mol/L dilute hydrochloric acid for 10 timesObtaining a polydopamine-coated porous graphite material;
and S3, adding 10g of aluminum chloride into 200g of toluene to prepare an aluminum chloride solution with the mass concentration of 5%, then adding 100g of polydopamine-coated porous graphite material, then adding ammonia water to adjust the pH value to 7, reacting at 120 ℃ for 1h, filtering after the reaction is finished, vacuum-drying at 80 ℃ for 24h, and sintering at the high temperature of 1200 ℃ for 1h under the inert atmosphere of argon gas to obtain the porous alumina/amorphous carbon-coated graphite composite material.
Comparative example 1
A preparation method of a quick-filling graphite composite material comprises the following steps:
s1, adding 100g of artificial graphite and 5g of sodium bicarbonate into a ball mill, uniformly mixing, transferring into a tubular furnace, introducing chlorine gas, reacting at the gas flow rate of 100mL/min and the reaction temperature of 270 ℃ for 60min, soaking for 24h by using 0.1mol/L dilute hydrochloric acid, and washing with deionized water to obtain porous graphite;
s2, adding 5g of aluminum chloride into 500g of ethanol to prepare an aluminum chloride solution with the mass concentration of 1%, then adding 100g of porous graphite material, then adding ammonia water to adjust the pH value to 7, reacting at 80 ℃ for 3 hours, filtering after the reaction is finished, then vacuum-drying at 80 ℃ for 48 hours, and sintering at high temperature under the inert atmosphere of argon at 900 ℃ for 3 hours to obtain the porous alumina coated graphite composite material.
Comparative example 2
A preparation method of a quick-filling graphite composite material comprises the following steps:
s1, adding 100g of artificial graphite and 5g of sodium bicarbonate into a ball mill, uniformly mixing, transferring into a tubular furnace, introducing chlorine gas, reacting at the gas flow rate of 100mL/min and the reaction temperature of 270 ℃ for 60min, soaking for 24h by using 0.1mol/L dilute hydrochloric acid, and washing with deionized water to obtain porous graphite;
s2, mixing 100g of porous graphite and 10g of Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 Adding 5g of polyaniline into a ball mill, and uniformly mixing to obtain a material A;
and S3, adding 5g of aluminum chloride into 500g of ethanol to prepare an aluminum chloride solution with the mass concentration of 1%, then adding 100g of the material A, then adding ammonia water to adjust the pH value to 7, reacting for 3 hours at 80 ℃, filtering after the reaction is finished, then drying for 48 hours at 80 ℃ in vacuum, and sintering at high temperature under the inert atmosphere of argon at 900 ℃ for 3 hours to obtain the porous alumina/amorphous carbon coated graphite composite material.
Comparative example 3
A preparation method of a quick-filling graphite composite material comprises the following steps:
s1, adding 100g of artificial graphite and 5g of sodium bicarbonate into a ball mill, uniformly mixing, transferring into a tubular furnace, introducing chlorine gas, reacting at the gas flow rate of 100mL/min and the reaction temperature of 270 ℃ for 60min, soaking for 24h by using 0.1mol/L dilute hydrochloric acid, and washing with deionized water to obtain porous graphite;
s2, mixing 5g of Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 Adding the solution into 100mL of 0.1mol/L dopamine aqueous solution, uniformly dispersing the solution to serve as a solvent, pressing porous graphite into a blocky structure to serve as a working electrode, taking a platinum electrode as a counter electrode, performing electrochemical deposition for 60min by adopting a constant pressure method at the voltage of 2V, and then washing the electrode for 10 times by adopting 0.1mol/L dilute hydrochloric acid to obtain a polydopamine-coated porous graphite material;
and S3, coating 100g of polydopamine on the porous graphite material, and sintering at the high temperature of 900 ℃ for 3 hours in an argon inert atmosphere to obtain the amorphous carbon coated graphite composite material.
The prepared graphite composite material was subjected to the following tests:
1. SEM test
SEM test of the porous alumina/amorphous carbon coated graphite composite material prepared in example 1 shows that the porous alumina/amorphous carbon coated graphite composite material prepared in example 1 has a granular structure, a particle size of 10-15 μm and a uniform size distribution, as shown in figure 1.
2. Physicochemical Properties and button cell test
(1) Testing physicochemical properties:
the tap density, the specific surface area, the powder conductivity and the powder OI value of the graphite composite materials prepared in examples 1-3 and comparative examples 1-3 are tested according to a testing method specified in the national standard GB/T-243357-2019 graphite cathode materials of lithium ion batteries;
(2) And (3) button cell testing: the graphite composite materials prepared in examples 1-3 and comparative examples 1-3 were used as negative electrode materials, and button cells were assembled as follows:
adding a binder, a conductive agent and a solvent into the negative electrode material, stirring and mixing uniformly to prepare negative electrode slurry, coating the negative electrode slurry on a copper foil, drying, rolling and cutting to prepare a negative electrode sheet, wherein the binder is polyvinylidene fluoride, the conductive agent is an SP conductive agent, the solvent is N-methylpyrrolidone, and the weight ratio of the negative electrode material to the conductive agent to the solvent is 95.
The lithium metal sheet is used as a counter electrode, a polyethylene film, a polypropylene film or a polyethylene-propylene composite film is used as a diaphragm, and LiPF is used 6 /EC+DEC（LiPF 6 The concentration of (1.3 mol/L) and the volume ratio of EC to DEC of 1:1) as electrolyte, and assembling the cell in an argon-filled glove box to obtain the button cell.
The prepared button cell is respectively arranged on a Wuhan blue electricity CT2001A type cell tester, and is charged and discharged at 0.1C multiplying power, the charging and discharging voltage range is 0.005V to 2.0V, and the first discharge capacity and the first discharge efficiency are measured. The rate discharge capacity of the catalyst at 2C was measured, and the rate performance (2C/0.1C) and the cycle performance (0.1C/0.1C, 100 weeks) were calculated.
The test results are shown in table 1:
TABLE 1 physicochemical Properties and button cell test results
As can be seen from the above table, the discharge capacity of the button cell using the graphite composite materials of examples 1 to 3 as the negative electrode material is significantly higher than that of comparative examples 1 to 3, which may be caused by doping the porous graphite material with the solid electrolyte, and the irreversible capacity of the graphite composite material is reduced by utilizing the characteristic of high conductivity of the solid electrolyte, so as to improve the first efficiency; meanwhile, the amorphous carbon obtained by sintering the polydopamine-coated porous graphite material prepared by electrochemical deposition has the characteristic of high density, and the tap density and the cycle performance of the graphite composite material are improved.
3. Pouch cell testing
The graphite composite materials of examples 1 to 3 and comparative examples 1 to 3 are respectively used as cathode materials to prepare cathodes, and a ternary material LiNi is used 1/3 Co 1/3 Mn 1/3 O 2 Preparing a positive electrode from a positive electrode material by using LiPF 6 /EC+DEC（LiPF 6 The concentration of (3) is 1.3mol/L, the volume ratio of EC to DEC is 1:1) is used as electrolyte, and celegard2400 is used as a diaphragm to prepare the 2Ah flexible package battery.
When the negative electrode is prepared, the binder, the conductive agent and the solvent are added into the negative electrode material, the negative electrode slurry is prepared by stirring and mixing uniformly, the slurry of the negative electrode slurry is coated on a copper foil, and the negative electrode sheet 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 negative electrode material, the conductive agent, the binder and the solvent is 95.
When the positive electrode is prepared, adding a binder, a conductive agent and a solvent into a positive electrode material, uniformly stirring and mixing to prepare positive electrode slurry, coating the positive electrode slurry on an aluminum foil, drying, rolling, and cutting to prepare a positive electrode sheet, wherein the binder is PVDF, the conductive agent is SP, the solvent is N-methylpyrrolidone, and the weight ratio of the positive electrode material to the conductive agent to the solvent is 93.
The assembled pouch cells were tested as follows:
(1) And (3) rate performance test: the charging and discharging voltage range is 2.8-4.2V, the testing temperature is 25 +/-3.0 ℃, the charging is respectively carried out at 1.0C, 2.0C, 3.0C and 5.0C, the discharging is carried out at 1.0C, the constant current ratio and the temperature of the battery under different charging modes are tested, and the results are shown in Table 2:
TABLE 2 Rate Performance test results
As can be seen from table 2, the rate charging performance of the pouch battery using the graphite composite material of examples 1 to 3 as the negative electrode is obviously improved in comparison with comparative examples 1 to 3, which indicates that the graphite composite material prepared by the preparation method of the present invention has good fast charging performance, and the reason for this is probably that the graphite composite material is doped with a solid electrolyte with high ionic conductivity and amorphous carbon formed by carbonizing poly dopamine deposited electrochemically, so that the graphite composite material has a low powder OI value, the dynamic performance of the graphite composite material is improved, the rate performance of the graphite composite material is improved, and the temperature rise of the battery using the graphite composite material as the negative electrode material in the charging process is reduced.
(2) And (3) testing cycle performance: the capacity retention rate was tested by performing 100, 300 and 500 charge-discharge cycles in sequence at a charge-discharge rate of 2C/2C and a voltage range of 2.8-4.2V, and the results are shown in Table 3:
TABLE 3 results of the cycle performance test
As can be seen from table 3, the cycle performance of the pouch battery using the graphite composite material of examples 1 to 3 as the negative electrode is obviously improved in comparison with comparative examples 1 to 3, which indicates that the graphite composite material prepared by the preparation method of the present invention has good cycle performance, and the reason for this is probably that the graphite composite material is doped with a solid electrolyte with high lithium ion content and amorphous carbon formed by carbonizing electrochemically deposited poly-dopamine, and the two cooperate with each other to provide sufficient lithium ions for the charge and discharge process and to ensure the stable structure of the battery negative electrode material during the charge and discharge process, thereby improving the cycle performance of the battery using the graphite composite material as the negative electrode material.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the quick-filling graphite composite material is characterized by comprising the following steps:
s1, uniformly mixing graphite and sodium bicarbonate, introducing oxidizing gas for reaction, and then carrying out acid washing to obtain porous graphite;
s2, taking a dopamine aqueous solution containing a solid electrolyte as a solution, taking porous graphite as a working electrode, taking a platinum electrode as a counter electrode, and performing electrochemical deposition by adopting a constant pressure method to obtain polydopamine-coated porous graphite;
and S3, adding the polydopamine coated porous graphite into an organic solvent containing aluminum chloride, reacting for 1-6h at 60-120 ℃, filtering, drying and sintering to obtain the porous alumina/amorphous carbon coated graphite material.
2. The preparation method of the quick-filling graphite composite material according to claim 1, wherein in the S1, the mass ratio of graphite to sodium bicarbonate is 100-10.
3. The preparation method of the rapid-filling graphite composite material as claimed in claim 1, wherein in the step S1, the mixing manner of the graphite and the sodium bicarbonate is ball milling.
4. The preparation method of the rapidly-filled graphite composite material according to claim 1, wherein in the step S1, the oxidizing gas is one of chlorine and sulfur dioxide, the flow rate of the oxidizing gas is 50-200mL/min, the reaction temperature is 200-300 ℃, and the reaction time is 30-300min.
5. The method for preparing the quick-charging graphite composite material according to claim 1, wherein in the S2, a solid electrolyte Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 、Li 6.5 La 3 Zr 1.5 Nb 0.5 O 12 、Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 、Li 6 La 3 Zr 1.0 Ta 1.0 O 12 One or more of (a).
6. The preparation method of the rapidly-filled graphite composite material according to claim 1, wherein in the step S2, the time of electrochemical deposition is 30-300min, and the voltage is 2V.
7. The method for preparing the rapidly-filled graphite composite material according to claim 1, wherein in the step S3, the mass concentration of aluminum chloride in the organic solvent containing aluminum chloride is 0.5% -5%, and the organic solvent is one of ethanol, acetone, toluene and dimethylformamide.
8. The preparation method of the rapidly-filled graphite composite material according to claim 1, wherein in the step S3, the mass ratio of the aluminum chloride to the polydopamine-coated porous graphite material is 1-10.
9. The preparation method of the rapidly-filled graphite composite material as claimed in claim 1, wherein in the step S3, the sintering is carried out in an inert gas atmosphere, the sintering temperature is 700-1200 ℃, and the sintering time is 1-6h.
10. A fast-charging graphite composite material, which is prepared by the preparation method of the fast-charging graphite composite material according to any one of claims 1 to 9.
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Effective date of registration: 20231207 Address after: 653100 Longquan District, high tech Zone, Yuxi City, Yunnan Province (Sanjie community, Dajie street, Jiangchuan District) Patentee after: Yunnan Kuntian New Energy Co.,Ltd. Address before: 050000 No. 8, kuntian Avenue, Suyang Township, Yuanshi County, Shijiazhuang City, Hebei Province Patentee before: Hebei kuntian new energy Co.,Ltd. |