CN116395684A - Method for preparing graphite for lithium battery at low temperature by using silver salt to catalyze coke - Google Patents
Method for preparing graphite for lithium battery at low temperature by using silver salt to catalyze coke Download PDFInfo
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- CN116395684A CN116395684A CN202310483320.6A CN202310483320A CN116395684A CN 116395684 A CN116395684 A CN 116395684A CN 202310483320 A CN202310483320 A CN 202310483320A CN 116395684 A CN116395684 A CN 116395684A
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- silver salt
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- coke
- lithium batteries
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- 239000000571 coke Substances 0.000 title claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 38
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 23
- 239000010439 graphite Substances 0.000 title claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002791 soaking Methods 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 239000007770 graphite material Substances 0.000 claims abstract description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical class [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 239000003245 coal Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical group OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 4
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- NBYLLBXLDOPANK-UHFFFAOYSA-M silver 2-carboxyphenolate hydrate Chemical compound C1=CC=C(C(=C1)C(=O)O)[O-].O.[Ag+] NBYLLBXLDOPANK-UHFFFAOYSA-M 0.000 claims description 4
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071536 silver acetate Drugs 0.000 claims description 4
- 229940045105 silver iodide Drugs 0.000 claims description 4
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 3
- 229940019931 silver phosphate Drugs 0.000 claims description 3
- 229910000161 silver phosphate Inorganic materials 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 abstract description 25
- 238000005087 graphitization Methods 0.000 abstract description 9
- 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
- 239000007773 negative electrode material Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021384 soft carbon Inorganic materials 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- ARNWQMJQALNBBV-UHFFFAOYSA-N lithium carbide Chemical compound [Li+].[Li+].[C-]#[C-] ARNWQMJQALNBBV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 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
- C01B32/205—Preparation
-
- 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
- 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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- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a method for preparing graphite for lithium batteries at low temperature by using silver salt to catalyze coke, which comprises the following steps: (1) Soaking the coke by adopting an ethanol solution, and then carrying out solid-liquid separation to obtain a product A; (2) Dispersing silver salt into glycol solution, adding a product A, reacting the obtained mixture at a first preset temperature for a first preset time, adding ammonia water, reacting at a second preset temperature for a second preset time, and carrying out solid-liquid separation to obtain a product B; (3) Calcining the product B in an inert atmosphere at 600-1200 ℃ for 4-10 hours, then soaking the product B in nitric acid solution, and carrying out solid-liquid separation to obtain the graphite material for lithium batteries. The invention can realize the low-temperature preparation of the graphite material, the graphitization degree of the prepared artificial graphite is more than 90 percent, and the prepared artificial graphite has high specific capacity, excellent multiplying power performance and good cycle stability when being used as a negative electrode material of a lithium ion battery.
Description
Technical Field
The invention relates to the field of preparation of lithium ion battery cathode materials, in particular to a method for preparing graphite for lithium batteries at a low temperature by using silver salt to catalyze coke.
Background
With the policy development requirements of "carbon neutralization" and "carbon peaking", fuel automobiles will be gradually replaced by new energy automobiles. In the new energy automobiles on the market at present, the lithium ion drive type occupies nine tenth of the market share. In a lithium ion battery, however, graphite is the negative electrode material thereof. The graphite consumption in the 2022 lithium battery automobile market is 72 ten thousand tons, and the multiplying power performance of the artificial graphite is superior to that of natural graphite, so that the artificial graphite accounts for two thirds of the share of the natural graphite. Commercial artificial graphite is produced by using a thermal phase transition technique to transform soft carbon into artificial graphite at temperatures above 2800 c, such as CN101648808B and US20020012845 A1. The high temperature process at 2800 ℃ is a high energy consumption process and the production process is full of danger, so that lowering the preparation temperature of the artificial graphite is of great importance.
CN108101043B adopts magnesium metal as catalyst, and at low temperature, the artificial graphite with graphitization degree higher than 90% is obtained, and the graphitization degree can meet the performance requirement of lithium battery negative electrode graphite, but the preparation process is still full of danger. Because commercial artificial graphite requires ton production, a large amount of magnesium catalyst is required. The magnesium emits a large amount of heat in the high-temperature catalysis process, and the huge heat emitted by the large amount of magnesium becomes a production safety hidden trouble. However, the graphitization degree of the artificial graphite (Carbon 75 (2014) 95-103) prepared by researchers under low temperature and low temperature conditions is lower than 50%, and the artificial graphite cannot meet the performance requirement of the lithium battery negative electrode graphite. Therefore, a technology for preparing artificial graphite at a mild low temperature needs to be developed, and the product can meet the performance requirement of the lithium battery anode material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing graphite for lithium batteries at low temperature by using silver salt to catalyze coke, and the performance of the method can meet the standard requirements of lithium-carbide ink. The graphite for lithium battery prepared by the method has high cycle specific capacity, good multiplying power performance and good cycle stability.
The invention is realized by the following technical scheme:
a method for preparing graphite for lithium batteries at low temperature by using silver salt to catalyze coke comprises the following steps:
(1) Soaking the coke by adopting an ethanol solution, and then carrying out solid-liquid separation to obtain a product A;
(2) Dispersing silver salt into glycol solution, adding a product A, reacting the obtained mixture at a first preset temperature for a first preset time, adding ammonia water, reacting at a second preset temperature for a second preset time, and carrying out solid-liquid separation to obtain a product B;
(3) Calcining the product B in an inert atmosphere at 600-1200 ℃ for 4-10 hours, then soaking the product B in nitric acid solution, and carrying out solid-liquid separation to obtain the graphite material for lithium batteries.
Preferably, the step (1) specifically comprises: and (3) soaking the coke in an ethanol solution, stirring under a heating condition, filtering, and drying to obtain a product A.
Preferably, in step (1), the coke is coal derived coke or petroleum derived coke.
Preferably, in step (1), the ratio of coke to ethanol solution is (1-100) g: (5-500) ml.
Preferably, in the step (2), the first preset temperature is 150 ℃, the first preset time is 5 hours, the second preset temperature is 180 ℃, and the second preset time is 3 hours.
Preferably, in step (2), the silver salt is silver iodide, silver acetate, silver phosphate, silver perchlorate or silver salicylate.
Preferably, in step (2), the ratio of silver salt to product A is (1-6) ml: (1-100) g.
Preferably, in the step (2), the concentration of ammonia is 2wt%, and the ratio of silver salt to ammonia is (1-6) ml: (1-10) ml.
Preferably, in step (2), the ratio of silver salt to glycol solution is (1-6) ml: (2-50) ml.
Preferably, in the step (3), the inert atmosphere is a nitrogen atmosphere.
Compared with the prior art, the invention has the following beneficial effects:
the coke adopted by the invention belongs to soft carbon materials, and can be soaked in ethanol solution to effectively remove non-lamellar structures in the soft carbon materials, so that the resistance is reduced when the subsequent calcination process is almost regular in thermodynamics; the silver salt and glycol form an atomic-level complex, the complex can be effectively diffused in coke, then dispersed nanometer small particles are formed under the action of ammonia water, and the uniformly distributed silver nanometer particles have a large number of dangling bonds, so that the complex has high catalytic activity, and can effectively catalyze the graphitization of the coke in the subsequent calcination process, thereby obtaining the lithium-electrode artificial graphite. Therefore, the invention can realize the low-temperature preparation of the graphite material, has simple process and good repeatability, can realize large-scale production, and the silver salt obtained by impurity removal can be effectively recycled for secondary use; the graphitization degree of the artificial graphite prepared by the method is more than 90%, and the artificial graphite has excellent electrochemical properties such as high specific capacity, excellent multiplying power performance, good cycling stability and the like when being used as a negative electrode material of a lithium ion battery.
Drawings
Fig. 1 is an X-ray diffraction chart of the lithium-grade artificial graphite prepared in examples 1 to 4 of the present invention.
FIG. 2 is a scanning electron microscope image of the lithium battery grade artificial graphite prepared in example 2 of the present invention.
Fig. 3 is a raman spectrum of the lithium battery grade artificial graphite prepared in example 3 of the present invention.
Fig. 4 is a graph showing the cycle stability of the lithium battery grade artificial graphite prepared in example 4 of the present invention as a lithium battery negative electrode material.
Detailed Description
For a further understanding of the present invention, the present invention is described below in conjunction with the following examples, which are provided to further illustrate the features and advantages of the present invention and are not intended to limit the claims of the present invention.
The invention relates to a method for preparing graphite for lithium batteries at low temperature by using silver salt to catalyze coke, which comprises the following steps:
(1) Soaking coke in ethanol solution, stirring under heating, filtering and drying to obtain a product A;
(2) Dispersing silver salt into glycol solution, stirring, adding the product A, continuously stirring the obtained mixture at 150 ℃ for 5 hours, slowly adding ammonia water, and continuously stirring at 180 ℃ for 3 hours; filtering and drying the product to obtain a product B;
(3) Calcining the product B for 4-10 hours in a nitrogen atmosphere at 600-1200 ℃, soaking the product B in a 0.1M nitric acid solution, and removing silver impurities to obtain the graphite material for the lithium battery, wherein the graphitization degree of the graphite material is more than 90%.
In the step (1), the coke is any one of coal derived coke and petroleum derived coke.
In the step (1), the ratio of the coke to the ethanol solution is (1-100) g: (5-500) ml, the heating temperature is preferably 80℃and the stirring time is preferably 5h.
In the step (2), the silver salt is any one of silver iodide, silver acetate, silver phosphate, silver perchlorate or silver salicylate.
In the step (2), the ratio of the silver salt to the glycol solution is (1-6) g: (2-50) ml; the concentration of ammonia is preferably 2wt%, and the ratio of silver salt to ammonia is (1-6) g: (1-10) ml; the ratio of silver salt to A product is (1-6) g: (1-100) g.
Example 1
(1) 1g of coal derived coke is soaked in 5ml of 50wt% ethanol solution, stirred for 5 hours at 80 ℃, filtered and dried to obtain a product A;
(2) Dispersing 1g of silver iodide into 2ml of glycol solution, stirring for 3 hours, adding 1g of A product, continuously stirring the obtained mixture at 150 ℃ for 5 hours, slowly adding 1ml of 2wt% ammonia water, and continuously stirring at 180 ℃ for 3 hours; filtering and drying the product to obtain a product B;
(3) Calcining the product B in 600 ℃ nitrogen atmosphere for 10 hours, soaking the product B in 0.1M nitric acid solution, and removing silver impurities to obtain the graphite material for lithium batteries.
Example 2
(1) Soaking 40g of petroleum derived coke in 100ml of 50wt% ethanol solution, stirring for 5 hours at 80 ℃, filtering and drying to obtain a product A;
(2) Dispersing 2g of silver acetate into 10ml of glycol solution, stirring for 3 hours, adding 10g of A product, continuously stirring the obtained mixture at 150 ℃ for 5 hours, slowly adding 3ml of 2wt% ammonia water, and continuously stirring at 180 ℃ for 3 hours; filtering and drying the product to obtain a product B;
(3) Calcining the product B for 8 hours in a nitrogen atmosphere at 800 ℃, soaking the product B in a 0.1M nitric acid solution, and removing silver impurities to obtain the graphite material for lithium batteries.
Example 3
(1) 80g of petroleum derived coke is soaked in 300ml of 50wt% ethanol solution, stirred for 5 hours at 80 ℃, filtered and dried to obtain a product A;
(2) Dispersing 5g of silver perchlorate into 30ml of glycol solution, stirring for 3 hours, adding 80g of A product, continuously stirring the obtained mixture at 150 ℃ for 5 hours, slowly adding 8ml of 2wt% ammonia water, and continuously stirring at 180 ℃ for 3 hours; filtering and drying the product to obtain a product B;
(3) Calcining the product B in nitrogen atmosphere at 1000 ℃ for 6 hours, soaking the product B in 0.1M nitric acid solution, and removing silver impurities to obtain the graphite material for lithium batteries.
Example 4
(1) 100g of coal derived coke is soaked in 500ml of 50wt% ethanol solution, stirred for 5 hours at 80 ℃, filtered and dried to obtain a product A;
(2) Dispersing 6g of silver salicylate into 50ml of glycol solution, stirring for 3 hours, adding 100g of A product, continuously stirring the mixture at 150 ℃ for 5 hours, slowly adding 10ml of 2wt% ammonia water, and continuously stirring at 180 ℃ for 3 hours; filtering and drying the product to obtain a product B;
(3) Calcining the product B for 4 hours in a nitrogen atmosphere at 1200 ℃, soaking the product B in a 0.1M nitric acid solution, and removing silver impurities to obtain the graphite material for lithium batteries.
Referring to the drawings, fig. 1 is an X-ray diffraction pattern of lithium-grade artificial graphite prepared in examples 1 to 4 of the present invention. Wherein the abscissa is the angle; the ordinate is the relative strength, with 30% by weight of elemental silicon as reference standard. From the graph, the (002) diffraction surface of the highest peak corresponding to the graphite is obtained, and the graphitization degree is 92% through formula calculation.
FIG. 2 is a scanning electron microscope image of the lithium battery grade artificial graphite prepared in example 2 of the present invention. From this, it can be seen that large sheets of artificial graphite were obtained.
Fig. 3 is a raman spectrum of the lithium battery grade artificial graphite prepared in example 3 of the present invention. Wherein the intensity of the ordered G peak is much higher than that of the disordered D peak, indicating that the product has a very high degree of graphitization.
Fig. 4 is a graph showing the cycling stability of the lithium battery grade artificial graphite prepared in example 4 of the present invention as a negative electrode material for a lithium ion battery. From the results, the specific capacity is not attenuated after 600 cycles, thus proving that the obtained low-temperature artificial graphite has good electrochemical performance as a lithium battery cathode
The invention is not limited to the specific embodiments set forth above, but rather, various equivalent modifications, equivalent substitutions, additions, deletions and rearrangements of parts may be made by those skilled in the art based on the principles of the invention and the specific embodiments set forth above, thereby creating more new embodiments.
Claims (10)
1. The method for preparing graphite for lithium batteries at low temperature by using silver salt to catalyze coke is characterized by comprising the following steps:
(1) Soaking the coke by adopting an ethanol solution, and then carrying out solid-liquid separation to obtain a product A;
(2) Dispersing silver salt into glycol solution, adding a product A, reacting the obtained mixture at a first preset temperature for a first preset time, adding ammonia water, reacting at a second preset temperature for a second preset time, and carrying out solid-liquid separation to obtain a product B;
(3) Calcining the product B in an inert atmosphere at 600-1200 ℃ for 4-10 hours, then soaking the product B in nitric acid solution, and carrying out solid-liquid separation to obtain the graphite material for lithium batteries.
2. The method for preparing graphite for lithium batteries at low temperature by using silver salt to catalyze coke according to claim 1, wherein the step (1) is specifically: and (3) soaking the coke in an ethanol solution, stirring under a heating condition, filtering, and drying to obtain a product A.
3. The method for preparing graphite for lithium batteries at low temperature by using silver salt catalyzed coke according to claim 1, wherein in the step (1), the coke is coal derived coke or petroleum derived coke.
4. The method for preparing graphite for lithium batteries at low temperature by using silver salt to catalyze coke according to claim 1, wherein in the step (1), the ratio of coke to ethanol solution is (1-100) g: (5-500) ml.
5. The method for preparing graphite for lithium batteries at low temperatures by using silver salt catalyzed coke according to claim 1, wherein in the step (2), the first preset temperature is 150 ℃, the first preset time is 5 hours, the second preset temperature is 180 ℃, and the second preset time is 3 hours.
6. The method for preparing graphite for lithium batteries at low temperature by using silver salt to catalyze coke according to claim 1, wherein in the step (2), the silver salt is silver iodide, silver acetate, silver phosphate, silver perchlorate or silver salicylate.
7. The method for preparing graphite for lithium batteries at low temperature by using silver salt to catalyze coke according to claim 1, wherein in the step (2), the ratio of silver salt to product a is (1-6) ml: (1-100) g.
8. The method for preparing graphite for lithium batteries at low temperature by using silver salt to catalyze coke according to claim 1, wherein in the step (2), the concentration of ammonia water is 2wt%, and the ratio of silver salt to ammonia water is (1-6) ml: (1-10) ml.
9. The method for preparing graphite for lithium batteries at low temperature by using silver salt to catalyze coke according to claim 1, wherein in the step (2), the ratio of silver salt to glycol solution is (1-6) ml: (2-50) ml.
10. The method for preparing graphite for lithium batteries at a low temperature by using silver salt-catalyzed coke according to claim 1, wherein in the step (3), the inert atmosphere is a nitrogen atmosphere.
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| US20120077020A1 (en) * | 2009-05-26 | 2012-03-29 | Kazuo Muramatsu | Carbon material and method for producing same |
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