CN111874901A - Method for manufacturing long-circulating graphite - Google Patents
Method for manufacturing long-circulating graphite Download PDFInfo
- Publication number
- CN111874901A CN111874901A CN202010762538.1A CN202010762538A CN111874901A CN 111874901 A CN111874901 A CN 111874901A CN 202010762538 A CN202010762538 A CN 202010762538A CN 111874901 A CN111874901 A CN 111874901A
- Authority
- CN
- China
- Prior art keywords
- artificial graphite
- precursor
- ball
- graphite
- cycle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- H01M4/58—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
-
- 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
Abstract
The invention discloses a method for manufacturing long-cycle graphite, which comprises the steps of adding agate beads with different sizes in a certain proportion into a ball mill, carrying out ball milling treatment on an artificial graphite precursor, removing irregular edges and corners on the microscopic surface of the precursor, improving the sphericity of powder, so that better graphite surface morphology can be obtained after subsequent high-temperature treatment, forming a tough SEI film on the surface of a negative electrode when the long-cycle graphite is applied to a lithium battery, reducing the irreversible capacity caused by repeated breakage and recombination of the SEI film, improving the coulombic efficiency during the cycle, and further prolonging the cycle life of the lithium battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a method for manufacturing long-cycle graphite.
Background
The lithium ion battery is a secondary battery which mainly depends on the movement of lithium ions between a positive electrode and a negative electrode to work. In the process of charging and discharging, Li + is inserted and extracted back and forth between the two electrodes, wherein during charging, Li + is extracted from the positive electrode and inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge. Lithium batteries are classified into lithium batteries and lithium ion batteries. Lithium ion batteries are used in mobile phones and notebook computers, and are commonly called as lithium batteries. The battery generally adopts a material containing lithium element as an electrode, and is a representative of modern high-performance batteries. The real lithium battery is rarely applied to daily electronic products due to high danger.
The graphite serving as the cathode material of the conventional lithium ion battery has the advantages of low charge-discharge voltage platform, high cycle stability, low cost and the like; the existing market demands require that the lithium ion battery has better cyclic charge and discharge capacity, so that the cyclic charge and discharge capacity of the lithium ion battery can be improved by optimizing the lithium intercalation capacity of graphite. The lithium intercalation ability of graphite can reduce capacity loss through surface modification.
To solve the above problems. Therefore, a method for manufacturing the long-cycle graphite is provided.
Disclosure of the invention
The invention aims to provide a method for manufacturing long-cycle graphite, which comprises the steps of adding agate beads with different sizes in a certain proportion into a ball mill, carrying out ball milling treatment on an artificial graphite precursor, removing irregular edges and corners on the microscopic surface of the precursor, improving the sphericity of powder, so that better graphite surface appearance can be obtained after subsequent high-temperature treatment, forming a tough SEI film on the surface of a negative electrode when the long-cycle graphite is applied to a lithium battery, and reducing irreversible capacity caused by repeated breakage and recombination of the SEI film, thereby solving the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme: a method for manufacturing long-cycle graphite comprises the following steps:
s1: pouring the artificial graphite precursor into an electric calcining furnace for calcining, wherein the calcining temperature is 1200-1400 ℃;
s2: crushing the artificial graphite precursor to the particle size of 1-20mm by a hammer crusher, grinding the crushed artificial graphite precursor to the particle size of 0.1-0.15 mm by a ball mill, and then mixing the artificial graphite precursor;
s3: kneading the artificial graphite precursor by a dry mixing method for 20-40 min;
s4: molding the artificial graphite precursor by molding equipment;
s5: roasting the artificial graphite precursor in a ring furnace at the roasting temperature of 1100-1300 ℃ for 20-35 days;
s6: dipping the artificial graphite precursor;
s7: graphitizing the artificial graphite precursor in a graphitizing furnace at the graphitization temperature of 2000-3000 ℃.
Preferably, the reasonable ball loading amount of the round balls is calculated by a formula Q which is 25% of pi D2 & L & psi & gamma, wherein Q is the reasonable ball loading amount, D is the inner diameter of the ball mill, L is the length of the inner diameter of the ball mill, psi is the filling rate of the ball mill, and gamma is the quasi-density of agate beads.
Preferably, balls with different size proportions are filled in the ball mill, and the balls are components made of agate beads.
Preferably, the diameter of the round ball is calculated by the formula D ═ k √ D, D is the diameter of the steel ball, k is the coefficient of the soft ore, k is 30, and the ratio of the large number to the small number of the round balls to the medium number is 4:3: 3.
Preferably, the ball milling time of the ball mill is 1-2h, and the air humidity during ball milling is 70-90%.
Compared with the prior art, the invention has the beneficial effects that: according to the scheme, the ball mill is used for adding agate beads with different sizes in a certain proportion, the artificial graphite precursor is subjected to ball milling treatment, irregular edges and corners on the microscopic surface of the precursor are removed, the sphericity of powder is improved, so that better graphite surface morphology can be obtained after subsequent high-temperature treatment, a tough SEI film can be formed on the surface of a negative electrode when the artificial graphite precursor is applied to a lithium battery, the irreversible capacity caused by repeated damage and recombination of the SEI film is reduced, the circulating coulombic efficiency is improved, and the cycle life of the lithium battery is further prolonged.
Drawings
FIG. 1 is a flow chart of a method of making long cycle graphite according to the present invention;
FIG. 2 is a graph comparing the discharge capacity retention rates of graphite according to 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 drawings in 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 obtained by a person skilled in the art without any inventive step based on the embodiments of the novel concept, are within the scope of the novel concept of the present invention.
Referring to fig. 1-2, a method for manufacturing long-cycle graphite includes the following steps:
the method comprises the following steps: and (3) pouring the artificial graphite precursor into an electric calcining furnace for calcining, wherein the calcining temperature is 1200-1400 ℃.
Step two: crushing an artificial graphite precursor to a particle size of 1-20mm by a hammer crusher, grinding the crushed artificial graphite precursor to a particle size of 0.1-0.15 mm by a ball mill, wherein the reasonable ball loading amount of balls is calculated by a formula Q which is 25% of pi D2 & L & psi & gamma, Q is the reasonable ball loading amount, D is the inner diameter of the ball mill, L is the length of the inner diameter of the ball mill, psi is the filling rate of the ball mill, gamma is the quasi-density of agate beads, balls with different sizes are filled in the ball mill, the diameter of the balls is calculated by a formula D which is k & check D, D is the diameter of steel balls, k is the coefficient of soft ore, k is 30, the ratio of large and small sizes of the balls is 4:3:3, the ball milling time of the ball mill is 1-2h, and the air humidity during ball milling is 70-90%, and the ball mill is used for adding agate balls with different sizes in a certain ratio, the artificial graphite precursor is subjected to ball milling treatment, irregular edges and corners on the microscopic surface of the precursor are removed, the sphericity of the powder is improved, so that better graphite surface morphology can be obtained after subsequent high-temperature treatment, a tough SEI film can be formed on the surface of a negative electrode when the artificial graphite precursor is applied to a lithium battery, the irreversible capacity caused by repeated damage and recombination of the SEI film is reduced, the coulombic efficiency during circulation is improved, the circulation life of the lithium battery is further prolonged, and the artificial graphite precursor is subjected to batching treatment.
Step three: the artificial graphite precursor is kneaded by a dry mixing method, and the dry mixing time is 20-40 min.
Step four: and (3) carrying out molding treatment on the artificial graphite precursor by using molding equipment.
Step five: roasting the artificial graphite precursor in a ring furnace at 1100-1300 deg.c for 20-35 days.
Step six: and (3) carrying out impregnation treatment on the artificial graphite precursor.
Step seven: graphitizing the artificial graphite precursor in a graphitizing furnace at the graphitization temperature of 2000-3000 ℃.
In summary, the following steps: according to the method for manufacturing the long-cycle graphite, the agate beads with different sizes are added in a certain proportion through the ball mill, the artificial graphite precursor is subjected to ball milling treatment, irregular edges and corners on the microscopic surface of the precursor are removed, the sphericity of powder is improved, so that a better graphite surface appearance can be obtained after subsequent high-temperature treatment, a tough SEI film can be formed on the surface of a negative electrode when the method is applied to a lithium battery, the irreversible capacity caused by repeated breakage and recombination of the SEI film is reduced, the coulomb efficiency during the cycle is improved, and the cycle life of the lithium battery is further prolonged.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although the novel embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A method for manufacturing long-cycle graphite is characterized by comprising the following steps: the manufacturing method of the long-cycle graphite comprises the following steps:
s1: pouring the artificial graphite precursor into an electric calcining furnace for calcining, wherein the calcining temperature is 1200-1400 ℃;
s2: crushing the artificial graphite precursor to the particle size of 1-20mm by a hammer crusher, grinding the crushed artificial graphite precursor to the particle size of 0.1-0.15 mm by a ball mill, and then mixing the artificial graphite precursor;
s3: kneading the artificial graphite precursor by a dry mixing method for 20-40 min;
s4: molding the artificial graphite precursor by molding equipment;
s5: roasting the artificial graphite precursor in a ring furnace at the roasting temperature of 1100-1300 ℃ for 20-35 days;
s6: dipping the artificial graphite precursor;
s7: graphitizing the artificial graphite precursor in a graphitizing furnace at the graphitization temperature of 2000-3000 ℃.
2. The method for manufacturing long cycle graphite according to claim 1, wherein: the reasonable ball loading amount of the balls is calculated by a formula Q which is 25 percent pi D2 & L & psi & gamma, wherein Q is the reasonable ball loading amount, D is the inner diameter of the ball mill, L is the length of the inner diameter of the ball mill, psi is the filling rate of the ball mill, and gamma is the quasi-density of agate beads.
3. The method for manufacturing long cycle graphite according to claim 1, wherein: the ball mill is internally filled with balls with different proportions, and the balls are components made of agate beads.
4. The method for manufacturing long cycle graphite according to claim 2, wherein: the diameter of the round ball is calculated by a formula D √ k √ D, D is the diameter of the steel ball, k is the coefficient of the soft ore, k is 30, and the ratio of the large quantity to the small quantity of the round ball to the medium quantity is 4:3: 3.
5. The method for manufacturing long cycle graphite according to claim 3, wherein: the ball milling time of the ball mill is 1-2h, and the air humidity during ball milling is 70-90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010762538.1A CN111874901A (en) | 2020-07-31 | 2020-07-31 | Method for manufacturing long-circulating graphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010762538.1A CN111874901A (en) | 2020-07-31 | 2020-07-31 | Method for manufacturing long-circulating graphite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111874901A true CN111874901A (en) | 2020-11-03 |
Family
ID=73205119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010762538.1A Pending CN111874901A (en) | 2020-07-31 | 2020-07-31 | Method for manufacturing long-circulating graphite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111874901A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112808260A (en) * | 2020-12-28 | 2021-05-18 | 江门市科恒实业股份有限公司 | Method for preparing cerium-zirconium solid solution by ball milling method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337605A (en) * | 2013-07-22 | 2013-10-02 | 深圳市斯诺实业发展有限公司永丰县分公司 | Method for preparing natural graphite cathode material of lithium ion battery by wet ball milling |
| CN103811759A (en) * | 2014-02-20 | 2014-05-21 | 深圳市贝特瑞新能源材料股份有限公司 | Modification method of natural graphite ball-milling machinery and modified natural graphite anode material |
| CN104085883A (en) * | 2014-07-09 | 2014-10-08 | 深圳市贝特瑞新能源材料股份有限公司 | Artificial graphite negative electrode material for lithium ion battery and preparation method thereof |
| CN105174251A (en) * | 2015-09-22 | 2015-12-23 | 成都炭素有限责任公司 | Preparation method of isostatic pressing formed graphite of ultra-thin structure |
| CN110203923A (en) * | 2019-04-24 | 2019-09-06 | 漳州巨铭石墨材料有限公司 | A kind of lithium ion battery negative material and preparation method thereof |
| CN110642247A (en) * | 2019-09-30 | 2020-01-03 | 广东凯金新能源科技股份有限公司 | Artificial graphite negative electrode material, preparation method thereof and lithium ion battery |
-
2020
- 2020-07-31 CN CN202010762538.1A patent/CN111874901A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337605A (en) * | 2013-07-22 | 2013-10-02 | 深圳市斯诺实业发展有限公司永丰县分公司 | Method for preparing natural graphite cathode material of lithium ion battery by wet ball milling |
| CN103811759A (en) * | 2014-02-20 | 2014-05-21 | 深圳市贝特瑞新能源材料股份有限公司 | Modification method of natural graphite ball-milling machinery and modified natural graphite anode material |
| CN104085883A (en) * | 2014-07-09 | 2014-10-08 | 深圳市贝特瑞新能源材料股份有限公司 | Artificial graphite negative electrode material for lithium ion battery and preparation method thereof |
| CN105174251A (en) * | 2015-09-22 | 2015-12-23 | 成都炭素有限责任公司 | Preparation method of isostatic pressing formed graphite of ultra-thin structure |
| CN110203923A (en) * | 2019-04-24 | 2019-09-06 | 漳州巨铭石墨材料有限公司 | A kind of lithium ion battery negative material and preparation method thereof |
| CN110642247A (en) * | 2019-09-30 | 2020-01-03 | 广东凯金新能源科技股份有限公司 | Artificial graphite negative electrode material, preparation method thereof and lithium ion battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112808260A (en) * | 2020-12-28 | 2021-05-18 | 江门市科恒实业股份有限公司 | Method for preparing cerium-zirconium solid solution by ball milling method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3553854A1 (en) | Lithium-ion battery and negative electrode material thereof | |
| CN103545497A (en) | Lithium ion battery cathode material with two-shell layer structure and preparation method thereof | |
| CN103187556B (en) | Lithium ion battery and its negative material, preparation method | |
| CN109786697A (en) | A kind of high voltage nickel-cobalt lithium manganate cathode material and preparation method thereof | |
| CN110176641A (en) | A kind of nanometer of LiF/Fe/ graphite anode mends the preparation method and applications of lithium slurry | |
| CN112421024A (en) | Coating method of positive electrode material for lithium ion battery | |
| CN111874901A (en) | Method for manufacturing long-circulating graphite | |
| CN104201374A (en) | High-capacity lithium ion battery cathode material and preparation method thereof | |
| CN106299330A (en) | A kind of preparation method improving anode material for lithium-ion batteries LiCoO2 current potential | |
| CN113097560A (en) | High-air-stability nanocrystalline sulfide solid electrolyte, solid-state battery and preparation method of solid-state battery | |
| CN102390825A (en) | Modified lithium iron phosphate material for lithium ion battery and preparation method thereof | |
| CN116190574A (en) | Composite negative electrode suitable for all-solid-state battery and preparation method thereof | |
| CN110921701A (en) | Production process of lithium ion battery negative electrode material | |
| CN102368552A (en) | High-performance anode material lithium cobalt oxide of lithium ion battery and preparation method thereof | |
| CN115101708A (en) | Secondary battery positive electrode material and sintering method, preparation method and application thereof | |
| EP3930058B1 (en) | Three-dimensional composite metal lithium negative electrode, metal lithium battery and apparatus | |
| CN115249799A (en) | Rosin-based nitrogen-doped coated hard carbon negative electrode material of sodium ion battery and preparation method of rosin-based nitrogen-doped coated hard carbon negative electrode material | |
| CN104157841A (en) | Preparation process of composite fiber electrode material for sodium-ion battery | |
| CN114744184A (en) | High-performance ternary cathode material and preparation method thereof | |
| CN115377407A (en) | Treatment process for positive electrode material of all-solid-state sodium ion battery | |
| CN114464785A (en) | Carbon-coated silicon monoxide negative electrode material, preparation method thereof and lithium ion battery | |
| CN203434237U (en) | Pole piece structure | |
| CN106876692B (en) | A kind of preparation method of lithium position silver-bearing copper chromium codope collaboration nitrogen sulfur doping coated modified carbon barium titanate lithium titanate cathode material | |
| CN107154492B (en) | A kind of the LNMO electrode material and preparation method of surface modification LATO | |
| CN104466152A (en) | Preparation method of lithium ion battery cathode material (lithium titanate) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201103 |
|
| RJ01 | Rejection of invention patent application after publication |