CN111777065A - Graphite modified material for lithium ion battery and preparation method thereof - Google Patents
Graphite modified material for lithium ion battery 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 82
- 239000010439 graphite Substances 0.000 title claims abstract description 69
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 69
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 15
- 239000008103 glucose Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- 229920000057 Mannan Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 9
- 238000003780 insertion Methods 0.000 abstract description 6
- 230000037431 insertion Effects 0.000 abstract description 6
- 239000007773 negative electrode material Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000003755 preservative agent Substances 0.000 description 5
- 230000002335 preservative effect Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 239000011852 carbon nanoparticle Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013458 LiC6 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- 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
- H01M4/362—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
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses a preparation method of a graphite modified material for a lithium ion battery, which comprises the following steps: dissolving 1.5-3.5 g of powdered sugar in 50ml of ethylene glycol, mechanically stirring, and performing ultrasonic treatment for later use; weighing a certain amount of spherical graphite, carrying out ultrasonic treatment in nitric acid, and washing with deionized water; dispersing the treated spherical graphite in a saccharide solvent, adding a dispersing agent into the saccharide solvent, carrying out ultrasonic treatment, and then violently stirring to obtain a suspension; putting the suspension into a high-pressure kettle for reaction, naturally cooling, and carrying out centrifugal separation and washing on the suspension; drying in an oven to obtain spherical graphite composite material powder modified by active carbon nano-ions; and drying the powder in an oven, and calcining at 500-900 ℃ in a nitrogen atmosphere to finally obtain the graphite modified material for the lithium ion battery. The graphite modified material has higher lithium insertion capacity and good cycle and conductivity when being used as a lithium battery negative electrode material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a graphite modified material for a lithium ion battery and a preparation method thereof.
Background
One of the main tasks for developing lithium ion secondary batteries is to find a special negative electrode material to replace lithium metal, in order to reduce the serious defects existing when lithium metal is used as a negative electrode, and the special negative electrode material has high working voltage, and simultaneously has enough high lithium intercalation amount and good lithium deintercalation reversibility, so as to ensure the requirements of high voltage, large capacity and long cycle life. Among the negative electrode materials, carbon materials such as petroleum coke, coal coke, graphite, mesophase carbon microspheres, organic matter pyrolysis carbon and the like are most successfully applied. The main advantages of the anode material are: the crystallinity is high, the discharge platform is in a plurality of nano materials, graphite is stable as a lithium ion secondary battery, the lithium insertion capacity is high, and the theoretical lithium insertion capacity of a compound LiC6 inserted between first-order graphite layers can reach 372 mAh/g. However, it also has significant disadvantages as an anode material.
The poor compatibility and high-rate charge and discharge performance with electrolyte solution are shown in that in the process of lithium insertion for the first time, solvated lithium ions are inserted into graphite layers before a good solid electrolyte phase interface film (SEI film) is formed on the graphite surface, and gas is generated by reduction and decomposition, so that the graphite layers are peeled off, the first charge and discharge efficiency is not high, and the stable cycle performance of the battery is also influenced.
Therefore, the graphite modified material for the lithium ion battery and the preparation method thereof are provided.
Disclosure of Invention
The invention mainly aims to provide a graphite modified material for a lithium ion battery and a preparation method thereof.
In order to achieve the aim, the invention provides a preparation method of a graphite modified material for a lithium ion battery, which comprises the following steps:
(1) preparing a saccharide solvent: dissolving 1.5-3.5 g of powdered sugar in 50ml of ethylene glycol, mechanically stirring, and performing ultrasonic treatment for later use;
(2) weighing a certain amount of spherical graphite, carrying out ultrasonic treatment in nitric acid, and washing with deionized water; dispersing the treated spherical graphite in a saccharide solvent, adding a dispersing agent into the saccharide solvent, and carrying out ultrasonic treatment; then stirring vigorously to obtain a suspension;
(3) putting the suspension into a high-pressure kettle for reaction, naturally cooling, and carrying out centrifugal separation and washing on the suspension; drying in an oven to obtain spherical graphite composite material powder modified by active carbon nano-ions;
(4) and drying the powder in an oven, and calcining at the temperature of 500-900 ℃ in a nitrogen atmosphere to finally obtain the graphite modified material for the lithium ion battery.
Preferably, the clear solution is obtained by mechanical stirring.
Preferably, the centrifugation is performed using a centrifuge.
Preferably, the concentration of the nitric acid is 1-3 mol/L.
Preferably, the powdered sugar is glucose, mannan or galactan.
Preferably, the dispersant is cetyl trimethyl ammonium bromide, polyacrylamide or methyl amyl alcohol.
Preferably, in the step (3), deionized water and ethanol are respectively used for washing, and the deionized water and the ethanol are respectively used for washing 3 times.
The first reversible capacity of the prepared graphite modified material for the lithium ion battery is more than 360mAh/g, the first coulombic efficiency is more than 86%, the capacity retention rate for 50 weeks is more than 90%, the expansion rate is less than 15%, and the electric conductivity is more than 3.5S/m.
Compared with the prior art, the invention has the following beneficial effects: the preparation method comprises the steps of modifying graphite, coating a layer of soft carbon material outside the graphite, then carrying out carbonization treatment, forming a soft carbon coating layer on the surface of the graphite after carbonization, and coating a hot solvent to prepare the carbon-coated graphite with a core-shell structure, wherein the cost is lower than that of chemical vapor deposition and the carbon-coated graphite is more uniform than that of solid phase coating; the high-pressure impregnation can not only uniformly coat the asphalt carbon on the surface of the graphite particles, but also fill the pores in the graphite particles, thereby improving the coating effect. The modified graphite not only can keep the characteristics of graphite, but also has higher lithium insertion capacity, the first charge-discharge efficiency is improved, and the cycle stability is obviously improved.
Drawings
FIG. 1 is a scanning electron micrograph of spheroidal graphite of example 1.
FIG. 2 is a scanning electron micrograph of the spherical graphite composite material of example 1.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example one
1.5g of glucose was weighed, dissolved in 50ml of ethylene glycol and mechanically stirred to obtain a clear solution. Then ultrasonic treatment is carried out for 30min, and the mixture is taken out and sealed by a preservative film for later use.
First, 3g of spherical graphite was weighed, sonicated in nitric acid at a concentration of 2mol/L for 10 minutes, and then washed with deionized water. The treated spheroidal graphite was dispersed in an aqueous glucose solution and cetyltrimethylammonium bromide was added to the glucose solution and sonicated for half an hour. After a further 10 minutes of vigorous stirring, the suspension was transferred to an autoclave and reacted at 180 ℃ for 4 hours. After the reaction, the autoclave was naturally cooled in air, the suspension was separated with the aid of a centrifuge, and washed three times with deionized water and ethanol, respectively. Drying for 4 hours at the temperature of 80 ℃ in an oven to obtain the powder of the spherical graphite composite material modified by the activated carbon nano particles, treating for 5 times, drying the obtained powder in the oven, and finally calcining for 3 hours at the temperature of 900 ℃ in a nitrogen atmosphere to obtain the graphite modified material for the lithium ion battery.
Example two
2.5g of glucose was weighed, dissolved in 50ml of ethylene glycol and mechanically stirred to obtain a clear solution. Then ultrasonic treatment is carried out for 30min, and the mixture is taken out and sealed by a preservative film for later use.
First, 3g of spherical graphite was weighed, sonicated in nitric acid at a concentration of 2mol/L for 10 minutes, and then washed with deionized water. The treated spheroidal graphite was dispersed in an aqueous glucose solution and cetyltrimethylammonium bromide was added to the glucose solution and sonicated for half an hour. After a further 10 minutes of vigorous stirring, the suspension was transferred to an autoclave and reacted at 180 ℃ for 4 hours. After the reaction, the autoclave was naturally cooled in air, the suspension was separated with the aid of a centrifuge, and washed three times with deionized water and ethanol, respectively. Drying the spherical graphite composite material for about 4 hours at 80 ℃ in an oven to obtain the spherical graphite composite material modified by the activated carbon nano particles, treating for 5 times, drying the obtained powder in the oven, and finally calcining for 3 hours at 500 ℃ in a nitrogen atmosphere to obtain the graphite modified material for the lithium ion battery.
EXAMPLE III
3.5g of glucose was weighed, dissolved in 50ml of ethylene glycol and mechanically stirred to obtain a clear solution. Then ultrasonic treatment is carried out for 30min, and the mixture is taken out and sealed by a preservative film for later use.
First, 3g of spherical graphite was weighed, sonicated in nitric acid at a concentration of 2mol/L for 10 minutes, and then washed with deionized water. The treated spheroidal graphite was dispersed in an aqueous glucose solution and cetyltrimethylammonium bromide was added to the glucose solution and sonicated for half an hour. After a further 10 minutes of vigorous stirring, the suspension was transferred to an autoclave and reacted at 180 ℃ for 4 hours. After the reaction, the autoclave was naturally cooled in air, the suspension was separated with the aid of a centrifuge, and washed three times with deionized water and ethanol, respectively. Drying in an oven at 80 ℃ for about 4 hours to obtain the spherical graphite composite material modified by the active carbon nano particles, treating for 5 times, drying the obtained powder in the oven, and finally calcining for 3 hours at 500 ℃ in a nitrogen atmosphere.
Example four
1.5g of mannan was weighed, dissolved in 50ml of ethylene glycol and mechanically stirred to obtain a clear solution. Then ultrasonic treatment is carried out for 30min, and the mixture is taken out and sealed by a preservative film for later use.
First, 3g of spherical graphite was weighed, sonicated in nitric acid at a concentration of 2mol/L for 10 minutes, and then washed with deionized water. The treated spheroidal graphite was dispersed in an aqueous glucose solution and polyacrylamide was added to the glucose solution and sonicated for half an hour. After a further 10 minutes of vigorous stirring, the suspension was transferred to an autoclave and reacted at 180 ℃ for 4 hours. After the reaction, the autoclave was naturally cooled in air, the suspension was separated with the aid of a centrifuge, and washed three times with deionized water and ethanol, respectively. Drying the spherical graphite composite material in an oven at 80 ℃ for about 4 hours to obtain the spherical graphite composite material modified by the active carbon nano particles. The treatment was carried out 5 times, and the obtained powder was dried in an oven and finally calcined at 500 ℃ for 3 hours under a nitrogen atmosphere.
EXAMPLE five
1.5g of galactan was weighed out, dissolved in 50ml of ethylene glycol and mechanically stirred to give a clear solution. Then ultrasonic treatment is carried out for 30min, and the mixture is taken out and sealed by a preservative film for later use.
First, 3g of spherical graphite was weighed, sonicated in nitric acid at a concentration of 2mol/L for 10 minutes, and then washed with deionized water. The treated spheroidal graphite was dispersed in an aqueous glucose solution and methyl amyl alcohol was added to the glucose solution and sonicated for half an hour. After a further 10 minutes of vigorous stirring, the suspension was transferred to an autoclave and reacted at 180 ℃ for 4 hours. After the reaction, the autoclave was naturally cooled in air, the suspension was separated with the aid of a centrifuge, and washed three times with deionized water and ethanol, respectively. Drying in an oven at 80 ℃ for about 4 hours to obtain the spherical graphite composite material modified by the active carbon nano particles, treating for 5 times, drying the obtained powder in the oven, and finally calcining for 3 hours at 500 ℃ in a nitrogen atmosphere.
Electrochemical cycling performance was tested using the following method: mixing a negative electrode material, a conductive agent and a binder in a solvent according to a mass ratio of 92:2:6, controlling the solid content to be 55%, coating the mixture on a copper foil current collector, and drying to obtain a negative electrode plate; and then assembling a 18650 cylindrical battery by using a conventional positive plate, 1mol/L LiPF6/EC + DMC (V/V is 1:1) electrolyte and a CeLgard2400 diaphragm, wherein the battery is charged and discharged at a constant current under the rate of 1C, and the charging and discharging voltage is limited to 2.75-4.2V. The first reversible capacity, the first coulombic efficiency, the 50-cycle capacity retention rate, the expansion rate, the conductivity and other indexes of the spherical graphite composite materials in the embodiments 1 to 5 are tested, and the results are shown in the following table:
TABLE 1
According to the test results of the examples 1 to 5 in the table 1, the first reversible capacity of the graphite modified material for the lithium ion battery is larger than 360mAh/g, the first coulombic efficiency is larger than 86%, the capacity retention rate for 50 weeks is larger than 90%, the expansion rate is lower than 15%, and the electric conductivity is larger than 3.5S/m. The conclusion can be drawn that the graphite modified material for the lithium ion battery prepared by the method has higher lithium insertion capacity when being used as the negative electrode material of the lithium ion battery, the first charge-discharge efficiency is improved, the cycle stability is obviously improved, and the range of the graphite composite material in the application field of the lithium ion battery is widened.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. A preparation method of a graphite modified material for a lithium ion battery is characterized by comprising the following steps:
(1) preparing a saccharide solvent: dissolving 1.5-3.5 g of powdered sugar in 50ml of ethylene glycol, mechanically stirring, and performing ultrasonic treatment for later use;
(2) weighing a certain amount of spherical graphite, carrying out ultrasonic treatment in nitric acid, and washing with deionized water; dispersing the treated spherical graphite in a saccharide solvent, adding a dispersing agent into the saccharide solvent, carrying out ultrasonic treatment, and then violently stirring to obtain a suspension;
(3) putting the suspension into a high-pressure kettle for reaction, naturally cooling, and carrying out centrifugal separation and washing on the suspension; drying in an oven to obtain spherical graphite composite material powder modified by active carbon nano-ions;
(4) and drying the powder in an oven, and calcining at the temperature of 500-900 ℃ in a nitrogen atmosphere to finally obtain the graphite modified material for the lithium ion battery.
2. The method for preparing the graphite modified material for lithium ion batteries according to claim 1, wherein the transparent solution is obtained by mechanical stirring.
3. The method for preparing the graphite modified material for the lithium ion battery according to claim 1, wherein a centrifuge is used for centrifugal separation.
4. The method for preparing the graphite modified material for the lithium ion battery according to claim 1, wherein the concentration of the nitric acid is 1-3 mol/L.
5. The method for preparing the graphite modified material for the lithium ion battery according to claim 1, wherein the sugar powder is glucose, mannan, or galactan.
6. The method for preparing the graphite modified material for the lithium ion battery according to claim 1, wherein the dispersing agent is cetyl trimethyl ammonium bromide, polyacrylamide or methyl amyl alcohol.
7. The method for preparing the graphite modified material for lithium ion batteries according to claim 1, wherein in the step (3), deionized water and ethanol are respectively used for washing, and the deionized water and the ethanol are respectively used for washing 3 times.
8. The graphite modified material for the lithium ion battery prepared by the preparation method of claims 1-7 is characterized in that the first reversible capacity of the prepared graphite modified material for the lithium ion battery is more than 360mAh/g, the first coulombic efficiency is more than 86%, the 50-week capacity retention rate is more than 90%, the expansion rate is less than 15%, and the electric conductivity is more than 3.5S/m.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113363447A (en) * | 2021-06-18 | 2021-09-07 | 广东凯金新能源科技股份有限公司 | Hard carbon composite graphite negative electrode material and preparation method thereof |
| CN113363448A (en) * | 2021-06-18 | 2021-09-07 | 广东凯金新能源科技股份有限公司 | Soft carbon composite graphite negative electrode material and preparation method thereof |
| CN113422030A (en) * | 2021-06-29 | 2021-09-21 | 贝特瑞新材料集团股份有限公司 | Negative electrode material and preparation method thereof, battery negative electrode and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050437A (en) * | 2009-10-29 | 2011-05-11 | 上海比亚迪有限公司 | Carbon composite material, and preparation method and application thereof |
| CN102544458A (en) * | 2011-12-30 | 2012-07-04 | 中聚電池研究院有限公司 | Preparation method of modified graphite negative electrode material of lithium ion power battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050437A (en) * | 2009-10-29 | 2011-05-11 | 上海比亚迪有限公司 | Carbon composite material, and preparation method and application thereof |
| CN102544458A (en) * | 2011-12-30 | 2012-07-04 | 中聚電池研究院有限公司 | Preparation method of modified graphite negative electrode material of lithium ion power battery |
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| CN113363447A (en) * | 2021-06-18 | 2021-09-07 | 广东凯金新能源科技股份有限公司 | Hard carbon composite graphite negative electrode material and preparation method thereof |
| CN113363448A (en) * | 2021-06-18 | 2021-09-07 | 广东凯金新能源科技股份有限公司 | Soft carbon composite graphite negative electrode material and preparation method thereof |
| CN113422030A (en) * | 2021-06-29 | 2021-09-21 | 贝特瑞新材料集团股份有限公司 | Negative electrode material and preparation method thereof, battery negative electrode and lithium ion battery |
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