CN116281939B - Hard carbon negative electrode material of battery and preparation method thereof - Google Patents
Hard carbon negative electrode material of battery and preparation method thereof Download PDFInfo
- Publication number
- CN116281939B CN116281939B CN202310081590.4A CN202310081590A CN116281939B CN 116281939 B CN116281939 B CN 116281939B CN 202310081590 A CN202310081590 A CN 202310081590A CN 116281939 B CN116281939 B CN 116281939B
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- battery
- negative electrode
- electrode material
- mixed solution
- 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.)
- Active
Links
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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/229—Lanthanum oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 a hard carbon negative electrode material of a battery and a preparation method thereof, belonging to the technical field of battery materials. Pretreating high sulfur coal to obtain a pretreated carbon source, carbonizing the pretreated carbon source to obtain a hard carbon precursor, mixing an organotin solution with a cerium nitrate solution and a lanthanum nitrate solution to obtain a mixed solution, adding the hard carbon precursor and a coating agent into the mixed solution, uniformly mixing, and carbonizing at a high temperature to obtain the battery hard carbon anode material. According to the invention, high sulfur coal is selected as a hard carbon source, sulfur elements are uniformly distributed, the pore canal structure is suitable for potassium ion intercalation/deintercalation, organic tin, cerium nitrate and lanthanum nitrate are introduced into tin oxide, cerium oxide and lanthanum oxide through carbonization, the problems of the first coulombic efficiency of the hard carbon negative electrode material of the battery are synergistically improved, the surface defects of the hard carbon negative electrode material are repaired by the coating agent, the specific surface area is reduced, and the first coulombic efficiency of the hard carbon negative electrode material of the battery is further improved.
Description
Technical Field
The invention belongs to the technical field of battery materials, and relates to a hard carbon negative electrode material of a battery and a preparation method thereof.
Background
The lithium ion secondary battery is widely applied to the fields of 3C consumer batteries, power batteries and energy storage batteries due to the advantages of good stability, high energy density, no memory effect and the like. The current commercial lithium ion secondary battery cathode material mainly comprises a graphite cathode, but the theoretical specific capacity of the graphite cathode is lower and is only 372mAh/g, and the high-rate continuous charge-discharge capability and the low-temperature performance are difficult to effectively improve. However, with the large-scale application of lithium ion batteries, the price and the resource limitation of lithium are becoming more and more a concern. In recent years, many new alternative energy storage batteries have been developed and rapidly developed, mainly including secondary batteries of sodium ion, potassium ion, magnesium ion, calcium ion, and the like.
The potassium ion battery has a plurality of advantages as a novel alternative energy storage battery, and the potassium source is rich in the crust and low in cost; the standard reduction potential of the potassium ion battery is closest to that of the lithium ion battery, so that the energy density is high; the electrolyte of the potassium ion battery has high electrochemical activity and is favorable for the transmission of ions and electrons. The currently reported research on the cathode materials of the potassium ion batteries is less, the focus of the research is focused on the carbon materials, however, the carbon cathode performance of the lithium ion battery and the sodium ion battery is usually poor due to the overlarge radius of potassium ions and the higher chemical activity of potassium.
The hard carbon is amorphous carbon difficult to graphitize, has larger layer spacing than a graphite negative electrode, has good rapid charge and discharge performance, and particularly has excellent low-temperature charge and discharge performance. However, due to the high specific surface area of the hard carbon and the porous structure of the material, the first efficiency of the material is low, the specific capacity is low, and one of the measures for improving the first efficiency of the hard carbon material is to perform surface coating of the material, and the current coating mainly improves the first efficiency of the material by coating amorphous carbon on the surface of the material, but has poor conductivity and limited first efficiency improvement range.
Chinese patent No. CN109301246B discloses a sulfur-doped hard carbon material, a method for preparing the same, and a potassium ion battery using the same as a negative electrode, wherein the hard carbon material has a porous structure, and sulfur atoms are at least partially distributed in the hard carbon material. The preparation method of the hard carbon material comprises the following steps:
(1) Pickling high sulfur coal, and then soaking in an alkaline solution to obtain a pre-product;
(2) Carrying out heat treatment on the pre-product in a protective atmosphere to obtain a hard carbon material;
(3) The hard carbon material is subjected to the processes of acid solution soaking, washing, filtering and drying. The invention takes high sulfur coal as raw material, the pore size of the prepared hard carbon material can meet the requirement of potassium ion intercalation/deintercalation, and simultaneously, sulfur element is self-doped on the surface of the material and in a carbon matrix in situ, thus endowing the material with new electrochemical activity and more ideal pore channel structure. The sulfur element in the carbon material prepared by the method is more uniformly distributed, and the production cost is lower.
However, in the invention, high sulfur coal is directly carbonized, and the obtained hard carbon contains more uniform sulfur element, but the high specific surface area of the hard carbon and the porous structure of the material thereof cause low initial coulomb efficiency and low specific capacity of the material, so that the coulomb efficiency of the hard carbon anode material needs to be further improved, and the electrical property of the hard carbon anode material needs to be improved.
Disclosure of Invention
The invention aims to provide a hard carbon negative electrode material of a battery and a preparation method thereof, and belongs to the technical field of battery materials. Pretreating high sulfur coal to obtain a pretreated carbon source, carbonizing the pretreated carbon source to obtain a hard carbon precursor, mixing an organotin solution with a cerium nitrate solution and a lanthanum nitrate solution to obtain a mixed solution, adding the hard carbon precursor and a coating agent into the mixed solution, uniformly mixing, and carbonizing at a high temperature to obtain the battery hard carbon anode material. According to the invention, high sulfur coal is selected as a hard carbon source, sulfur elements are uniformly distributed, the pore canal structure is suitable for potassium ion intercalation/deintercalation, organic tin, cerium nitrate and lanthanum nitrate are introduced into tin oxide, cerium oxide and lanthanum oxide through carbonization, the problems of the first coulombic efficiency of the hard carbon negative electrode material of the battery are synergistically improved, the surface defects of the hard carbon negative electrode material are repaired by the coating agent, the specific surface area is reduced, and the first coulombic efficiency of the hard carbon negative electrode material of the battery is further improved.
The aim of the invention can be achieved by the following technical scheme:
a method for preparing a hard carbon negative electrode material of a battery, comprising the following steps:
(1) Soaking high sulfur coal in acid liquor, taking out, drying and crushing to obtain a pretreated carbon source;
(2) Carbonizing a pretreated carbon source in an inert gas atmosphere to obtain a hard carbon precursor;
(3) Dissolving organic tin in an organic solvent, then adding a cerium nitrate aqueous solution and a lanthanum nitrate aqueous solution, and mixing to obtain a mixed solution;
(4) And adding the hard carbon precursor and the coating agent into the mixed solution, stirring and uniformly mixing, and carbonizing to obtain the hard carbon anode material of the battery.
As a preferable technical scheme of the invention, the sulfur content of the high sulfur coal in the step (1) is 6-9wt%.
As a preferable technical scheme of the invention, the acid liquor in the step (1) is sulfuric acid aqueous solution with the concentration of 5-10 mol/L.
As a preferable technical scheme of the invention, the carbonization treatment in the step (2) is to heat up to 500-1000 ℃ at a heating rate of 2-5 ℃/min, and keep the temperature for 2-4h.
As a preferable technical scheme of the invention, the organic solvent in the step (3) is at least one of ethanol, triethanolamine and ethylene glycol ether.
As a preferable embodiment of the present invention, the organotin in the step (3) is at least one of dibutyltin, dimethyltin, dioctyltin, tetraphenyltin, tributyltin, and triphenyltin.
As a preferable technical scheme of the invention, in the step (3), the mass ratio of the organic tin, the cerium nitrate and the lanthanum nitrate in the mixed solution is 1:0.2-0.6:0.1-0.3, and the total concentration of the organic tin, the cerium nitrate and the lanthanum nitrate in the mixed solution is 8-15mol/L.
As a preferable technical scheme of the invention, the coating agent in the step (4) is at least one of furan resin, phenolic resin, polypyrrole, polythiophene, petroleum asphalt, coal asphalt, heavy tar, coumarone resin, polystyrene, polyacrylonitrile, polyvinyl chloride, polymethyl methacrylate and polycarbonate.
As a preferable technical scheme of the invention, the mass ratio of the hard carbon precursor, the coating agent and the mixed solution in the step (4) is 1:0.3-0.7:15-25.
The battery hard carbon anode material prepared by the preparation method is prepared.
The invention has the beneficial effects that:
(1) The invention selects the high sulfur coal as the hard carbon source, and compared with the hard carbon material prepared by externally introducing sulfur element, the high sulfur coal is adopted as the carbon source, the sulfur element distribution is more uniform, the externally introducing sulfur element is not needed, the pore canal structure is suitable for the intercalation/deintercalation of potassium ion, and the invention is suitable for preparing the anode material of the potassium ion battery;
(2) According to the invention, tin oxide, cerium oxide and lanthanum oxide are introduced into the organic tin, cerium nitrate and lanthanum nitrate through carbonization processes, so that the problem of the first coulombic efficiency of the hard carbon negative electrode material of the battery is synergistically improved, the surface defect of the hard carbon negative electrode material is repaired by the coating agent, the specific surface area is reduced, and the first coulombic efficiency of the hard carbon negative electrode material of the battery is further improved;
(3) The invention takes high sulfur coal as a carbon source of hard carbon, has high production efficiency and low production cost.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description is given below with reference to the embodiments, structures, features and effects according to the present invention.
Example 1
A method for preparing a hard carbon negative electrode material of a battery, comprising the following steps:
(1) Adding high-sulfur coal with the sulfur content of 6.5wt% into a sulfuric acid solution with the concentration of 5mol/L, soaking, taking out, drying and crushing to obtain a pretreated carbon source;
(2) Heating a pretreated carbon source to 850 ℃ at a heating rate of 3 ℃/min in an inert gas atmosphere, and carbonizing for 2.6 hours to obtain a hard carbon precursor;
(3) Dissolving dibutyl tin in ethanol, then adding a cerium nitrate aqueous solution and a lanthanum nitrate aqueous solution, and mixing to obtain a mixed solution, wherein the mass ratio of dibutyl tin to cerium nitrate to lanthanum nitrate in the mixed solution is 1:0.3:0.1, and the total concentration of dibutyl tin to cerium nitrate to lanthanum nitrate is 9mol/L;
(4) And adding the hard carbon precursor and the petroleum asphalt into the mixed solution, controlling the mass ratio of the hard carbon precursor to the petroleum asphalt to be 1:0.4:17, stirring and uniformly mixing, and carbonizing to obtain the battery hard carbon anode material.
Example 2
A method for preparing a hard carbon negative electrode material of a battery, comprising the following steps:
(1) Adding high-sulfur coal with the sulfur content of 8wt% into sulfuric acid solution with the concentration of 7mol/L, soaking, taking out, drying and crushing to obtain a pretreated carbon source;
(2) Heating a pretreated carbon source to 800 ℃ at a heating rate of 2.6 ℃/min in an inert gas atmosphere, and carbonizing for 3 hours to obtain a hard carbon precursor;
(3) Dissolving dioctyltin in triethanolamine, adding cerium nitrate aqueous solution and lanthanum nitrate aqueous solution, and mixing to obtain a mixed solution, wherein the mass ratio of dioctyltin, cerium nitrate and lanthanum nitrate in the mixed solution is 1:0.2:0.3, and the total concentration of dioctyltin, cerium nitrate and lanthanum nitrate is 8.6mol/L;
(4) And adding the hard carbon precursor and the furan resin into the mixed solution, controlling the mass ratio of the hard carbon precursor to the furan resin to the mixed solution to be 1:0.3:18, stirring and uniformly mixing, and carbonizing to obtain the battery hard carbon anode material.
Example 3
A method for preparing a hard carbon negative electrode material of a battery, comprising the following steps:
(1) Adding high-sulfur coal with the sulfur content of 7.3 weight percent into 8mol/L sulfuric acid solution for soaking, taking out, drying and crushing to obtain a pretreated carbon source;
(2) Heating a pretreated carbon source to 960 ℃ at a heating rate of 4 ℃/min in an inert gas atmosphere, and carbonizing for 2 hours to obtain a hard carbon precursor;
(3) Dissolving tetraphenyltin in ethylene glycol ether, adding a cerium nitrate aqueous solution and a lanthanum nitrate aqueous solution, and mixing to obtain a mixed solution, wherein the mass ratio of the tetraphenyltin to the cerium nitrate to the lanthanum nitrate in the mixed solution is 1:0.5:0.2, and the total concentration of the tetraphenyltin to the cerium nitrate to the lanthanum nitrate is 11mol/L;
(4) And adding the hard carbon precursor and the polyacrylonitrile into the mixed solution, controlling the mass ratio of the hard carbon precursor to the polyacrylonitrile to the mixed solution to be 1:0.7:19, stirring and uniformly mixing, and carbonizing to obtain the battery hard carbon anode material.
Example 4
A method for preparing a hard carbon negative electrode material of a battery, comprising the following steps:
(1) Adding high-sulfur coal with the sulfur content of 8.4wt% into a sulfuric acid solution with the concentration of 9mol/L, soaking, taking out, drying and crushing to obtain a pretreated carbon source;
(2) Heating a pretreated carbon source to 880 ℃ at a heating rate of 3.9 ℃/min in an inert gas atmosphere, and carbonizing for 3 hours to obtain a hard carbon precursor;
(3) Dissolving tributyltin in ethanol, then adding a cerium nitrate aqueous solution and a lanthanum nitrate aqueous solution, and mixing to obtain a mixed solution, wherein the mass ratio of tributyltin, cerium nitrate and lanthanum nitrate in the mixed solution is 1:0.6:0.1, and the total concentration of tributyltin, cerium nitrate and lanthanum nitrate is 13mol/L;
(4) Adding the hard carbon precursor and polymethyl methacrylate into the mixed solution, controlling the mass ratio of the hard carbon precursor to the polymethyl methacrylate to the mixed solution to be 1:0.5:22, stirring and uniformly mixing, and carbonizing to obtain the hard carbon anode material of the battery.
Example 5
A method for preparing a hard carbon negative electrode material of a battery, comprising the following steps:
(1) Adding high-sulfur coal with the sulfur content of 9wt% into 8.8mol/L sulfuric acid solution for soaking, taking out, drying and crushing to obtain a pretreated carbon source;
(2) Heating a pretreated carbon source to 1000 ℃ at a heating rate of 5 ℃/min in an inert gas atmosphere, and carbonizing for 4 hours to obtain a hard carbon precursor;
(3) Dissolving triphenyltin in triethanolamine, then adding a cerium nitrate aqueous solution and a lanthanum nitrate aqueous solution, and mixing to obtain a mixed solution, wherein the mass ratio of the triphenyltin to the cerium nitrate to the lanthanum nitrate in the mixed solution is 1:0.4:0.3, and the total concentration of the triphenyltin to the cerium nitrate to the lanthanum nitrate is 15mol/L;
(4) Adding the hard carbon precursor and the coumarone resin into the mixed solution, controlling the mass ratio of the hard carbon precursor to the coumarone resin to the mixed solution to be 1:0.3:25, stirring and uniformly mixing, and carbonizing to obtain the hard carbon anode material of the battery.
Comparative example 1
A method for preparing a hard carbon negative electrode material of a battery, comprising the following steps:
(1) Adding high-sulfur coal with the sulfur content of 9wt% into 8.8mol/L sulfuric acid solution for soaking, taking out, drying and crushing to obtain a pretreated carbon source;
(2) And in an inert gas atmosphere, heating the pretreated carbon source to 1000 ℃ at a heating rate of 5 ℃/min for carbonization treatment for 4 hours, and obtaining the hard carbon cathode material of the battery.
Comparative example 2
A method for preparing a hard carbon negative electrode material of a battery, comprising the following steps:
(1) Adding high-sulfur coal with the sulfur content of 9wt% into 8.8mol/L sulfuric acid solution for soaking, taking out, drying and crushing to obtain a pretreated carbon source;
(2) Heating a pretreated carbon source to 1000 ℃ at a heating rate of 5 ℃/min in an inert gas atmosphere, and carbonizing for 4 hours to obtain a hard carbon precursor;
(3) Dissolving triphenyltin in triethanolamine, then adding a cerium nitrate aqueous solution and a lanthanum nitrate aqueous solution, and mixing to obtain a mixed solution, wherein the mass ratio of the triphenyltin to the cerium nitrate to the lanthanum nitrate in the mixed solution is 1:0.4:0.3, and the total concentration of the triphenyltin to the cerium nitrate to the lanthanum nitrate is 15mol/L;
(4) And adding the hard carbon precursor into the mixed solution, controlling the mass ratio of the hard carbon precursor to the mixed solution to be 1:25, stirring and uniformly mixing, and carbonizing to obtain the battery hard carbon anode material.
Comparative example 3
A method for preparing a hard carbon negative electrode material of a battery, comprising the following steps:
(1) Adding high-sulfur coal with the sulfur content of 9wt% into 8.8mol/L sulfuric acid solution for soaking, taking out, drying and crushing to obtain a pretreated carbon source;
(2) Heating a pretreated carbon source to 1000 ℃ at a heating rate of 5 ℃/min in an inert gas atmosphere, and carbonizing for 4 hours to obtain a hard carbon precursor;
(3) And (3) mixing and stirring the hard carbon precursor and the coumarone resin uniformly, controlling the mass ratio of the hard carbon precursor to the coumarone resin to be 1:0.3, and carbonizing after stirring and mixing uniformly to obtain the hard carbon anode material of the battery.
Comparative example 4
A method for preparing a hard carbon negative electrode material of a battery, comprising the following steps:
(1) Adding high-sulfur coal with the sulfur content of 9wt% into 8.8mol/L sulfuric acid solution for soaking, taking out, drying and crushing to obtain a pretreated carbon source;
(2) Heating a pretreated carbon source to 1000 ℃ at a heating rate of 5 ℃/min in an inert gas atmosphere, and carbonizing for 4 hours to obtain a hard carbon precursor;
(3) Dissolving triphenyltin in triethanolamine to obtain a triphenyltin solution, wherein the concentration of the triphenyltin is 15mol/L;
(4) Adding the hard carbon precursor and the coumarone resin into the triphenyltin solution, controlling the mass ratio of the hard carbon precursor to the coumarone resin to the triphenyltin solution to be 1:0.3:25, stirring and uniformly mixing, and carbonizing to obtain the battery hard carbon anode material.
Comparative example 5
A method for preparing a hard carbon negative electrode material of a battery, comprising the following steps:
(1) Adding high-sulfur coal with the sulfur content of 9wt% into 8.8mol/L sulfuric acid solution for soaking, taking out, drying and crushing to obtain a pretreated carbon source;
(2) Heating a pretreated carbon source to 1000 ℃ at a heating rate of 5 ℃/min in an inert gas atmosphere, and carbonizing for 4 hours to obtain a hard carbon precursor;
(3) Dissolving triphenyltin in triethanolamine, then adding a cerium nitrate aqueous solution, and mixing to obtain a mixed solution, wherein the mass ratio of the triphenyltin to the cerium nitrate in the mixed solution is 1:0.7, and the total concentration of the triphenyltin and the cerium nitrate is 15mol/L;
(4) Adding the hard carbon precursor and the coumarone resin into the mixed solution, controlling the mass ratio of the hard carbon precursor to the coumarone resin to the mixed solution to be 1:0.3:25, stirring and uniformly mixing, and carbonizing to obtain the hard carbon anode material of the battery.
Comparative example 6
A method for preparing a hard carbon negative electrode material of a battery, comprising the following steps:
(1) Adding high-sulfur coal with the sulfur content of 9wt% into 8.8mol/L sulfuric acid solution for soaking, taking out, drying and crushing to obtain a pretreated carbon source;
(2) Heating a pretreated carbon source to 1000 ℃ at a heating rate of 5 ℃/min in an inert gas atmosphere, and carbonizing for 4 hours to obtain a hard carbon precursor;
(3) Dissolving triphenyltin in triethanolamine, adding a lanthanum nitrate aqueous solution, and mixing to obtain a mixed solution, wherein the mass ratio of the triphenyltin to the lanthanum nitrate in the mixed solution is 1:0.7, and the total concentration of the triphenyltin and the lanthanum nitrate is 15mol/L;
(4) Adding the hard carbon precursor and the coumarone resin into the mixed solution, controlling the mass ratio of the hard carbon precursor to the coumarone resin to the mixed solution to be 1:0.3:25, stirring and uniformly mixing, and carbonizing to obtain the hard carbon anode material of the battery.
Comparative example 7
A method for preparing a hard carbon negative electrode material of a battery, comprising the following steps:
(1) Adding high-sulfur coal with the sulfur content of 9wt% into 8.8mol/L sulfuric acid solution for soaking, taking out, drying and crushing to obtain a pretreated carbon source;
(2) Heating a pretreated carbon source to 1000 ℃ at a heating rate of 5 ℃/min in an inert gas atmosphere, and carbonizing for 4 hours to obtain a hard carbon precursor;
(3) Dissolving cerium nitrate and lanthanum nitrate in deionized water to obtain a mixed solution, wherein the mass ratio of the cerium nitrate to the lanthanum nitrate in the mixed solution is 1.4:0.3, and the total concentration of the cerium nitrate and the lanthanum nitrate is 15mol/L;
(4) Adding the hard carbon precursor and the coumarone resin into the mixed solution, controlling the mass ratio of the hard carbon precursor to the coumarone resin to the mixed solution to be 1:0.3:25, stirring and uniformly mixing, and carbonizing to obtain the hard carbon anode material of the battery.
Performance testing
The hard carbon negative electrode materials for batteries prepared in examples 1 to 5 and comparative examples 1 to 7 were subjected to the following performance tests:
(1) Testing charge and discharge performance, namely assembling the prepared hard carbon cathode material of the battery into a button battery, and testing the performance of the battery by adopting blue electricity under the current density of 0.1A/g;
(2) Bet specific surface area test, using Bei Shide specific surface area tester to test specific surface area;
specific test results are shown in table 1 below:
as can be seen from the test results in Table 1, in comparative example 1, on the basis of example 5, the electrical properties of the hard carbon material are obviously reduced without adding the mixed solution and the coating agent, and the Bet specific surface area is obviously increased; comparative example 2, without the addition of a coating agent based on example 5, has reduced electrical properties and increased Bet specific surface area; comparative example 3, in which the electrical properties were lowered and the Bet specific surface area was increased without adding the mixed solution based on example 5; comparative example 4, which does not add cerium nitrate and lanthanum nitrate based on example 5, has reduced electrical properties and increased Bet specific surface area; comparative example 5, comparative example 6 and comparative example 7, in which lanthanum nitrate, cerium nitrate and triphenyltin were not added, respectively, had decreased electrical properties and increased Bet specific surface area.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (5)
1. The preparation method of the hard carbon negative electrode material of the battery is characterized by comprising the following steps of:
(1) Soaking high sulfur coal in acid liquor, taking out, drying and crushing to obtain a pretreated carbon source;
(2) Carbonizing a pretreated carbon source in an inert gas atmosphere to obtain a hard carbon precursor;
(3) Dissolving organic tin in an organic solvent, then adding a cerium nitrate aqueous solution and a lanthanum nitrate aqueous solution, and mixing to obtain a mixed solution;
(4) Adding the hard carbon precursor and the coating agent into the mixed solution, stirring and uniformly mixing, and carbonizing to obtain a hard carbon anode material of the battery;
the organic tin in the step (3) is at least one of dibutyl tin, dimethyl tin, dioctyl tin, tetraphenyl tin, tributyl tin and triphenyl tin;
the mass ratio of the organic tin, the cerium nitrate and the lanthanum nitrate in the mixed solution in the step (3) is 1:0.2-0.6:0.1-0.3, and the total concentration of the organic tin, the cerium nitrate and the lanthanum nitrate in the mixed solution is 8-15mol/L;
the coating agent in the step (4) is at least one of furan resin, phenolic resin, polypyrrole, polythiophene, petroleum asphalt, coal tar pitch, heavy tar, coumarone resin, polystyrene, polyacrylonitrile, polyvinyl chloride, polymethyl methacrylate and polycarbonate;
and (3) the mass ratio of the hard carbon precursor to the coating agent to the mixed solution in the step (4) is 1:0.3-0.7:15-25.
2. The method for preparing a hard carbon negative electrode material for a battery according to claim 1, wherein the sulfur content of the high sulfur coal in the step (1) is 6-9wt%.
3. The method for preparing the hard carbon negative electrode material of the battery, according to claim 1, wherein the acid solution in the step (1) is an aqueous sulfuric acid solution with a concentration of 5-10 mol/L.
4. The method for preparing a hard carbon negative electrode material for a battery according to claim 1, wherein the carbonization treatment in the step (2) is to raise the temperature to 500-1000 ℃ at a heating rate of 2-5 ℃/min, and keep the temperature for 2-4 hours.
5. The method for preparing a hard carbon negative electrode material of a battery according to claim 1, wherein the organic solvent in the step (3) is at least one of ethanol, triethanolamine and ethylene glycol ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310081590.4A CN116281939B (en) | 2023-02-08 | 2023-02-08 | Hard carbon negative electrode material of battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310081590.4A CN116281939B (en) | 2023-02-08 | 2023-02-08 | Hard carbon negative electrode material of battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116281939A CN116281939A (en) | 2023-06-23 |
| CN116281939B true CN116281939B (en) | 2023-09-08 |
Family
ID=86798743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310081590.4A Active CN116281939B (en) | 2023-02-08 | 2023-02-08 | Hard carbon negative electrode material of battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116281939B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103094528A (en) * | 2013-01-09 | 2013-05-08 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon cathode material for lithium ion power and energy storage battery and preparation method of hard carbon cathode material |
| CN106232226A (en) * | 2014-12-05 | 2016-12-14 | 日清纺控股株式会社 | C catalyst, electrode and battery |
| CN107032350A (en) * | 2017-04-21 | 2017-08-11 | 广东韩研活性炭制造有限公司 | A kind of electrode of super capacitor activated carbon and preparation method thereof |
| WO2022000070A1 (en) * | 2020-06-30 | 2022-01-06 | Atlas Power Generation Inc. | Energy storage devices, components and materials thereof, and methods therefor |
| CN114420927A (en) * | 2022-01-24 | 2022-04-29 | 蜂巢能源科技股份有限公司 | Negative electrode material, preparation method thereof and negative electrode plate |
| CN114927675A (en) * | 2022-06-30 | 2022-08-19 | 宜春瑞富特新能源材料技术有限公司 | Composite metal-coated silicon carbide-based negative electrode material and preparation method and application thereof |
| CN115566170A (en) * | 2022-10-19 | 2023-01-03 | 晖阳(贵州)新能源材料有限公司 | Preparation method of high-energy-density quick-charging lithium ion battery cathode material |
-
2023
- 2023-02-08 CN CN202310081590.4A patent/CN116281939B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103094528A (en) * | 2013-01-09 | 2013-05-08 | 深圳市贝特瑞新能源材料股份有限公司 | Hard carbon cathode material for lithium ion power and energy storage battery and preparation method of hard carbon cathode material |
| CN106232226A (en) * | 2014-12-05 | 2016-12-14 | 日清纺控股株式会社 | C catalyst, electrode and battery |
| CN107032350A (en) * | 2017-04-21 | 2017-08-11 | 广东韩研活性炭制造有限公司 | A kind of electrode of super capacitor activated carbon and preparation method thereof |
| WO2022000070A1 (en) * | 2020-06-30 | 2022-01-06 | Atlas Power Generation Inc. | Energy storage devices, components and materials thereof, and methods therefor |
| CN114420927A (en) * | 2022-01-24 | 2022-04-29 | 蜂巢能源科技股份有限公司 | Negative electrode material, preparation method thereof and negative electrode plate |
| CN114927675A (en) * | 2022-06-30 | 2022-08-19 | 宜春瑞富特新能源材料技术有限公司 | Composite metal-coated silicon carbide-based negative electrode material and preparation method and application thereof |
| CN115566170A (en) * | 2022-10-19 | 2023-01-03 | 晖阳(贵州)新能源材料有限公司 | Preparation method of high-energy-density quick-charging lithium ion battery cathode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116281939A (en) | 2023-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112225194B (en) | Hard carbon material and preparation method and application thereof | |
| CN112397715B (en) | Hard carbon material, preparation method thereof and sodium ion battery | |
| CN109755540B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN107579250B (en) | Composite carbon material conductive agent | |
| CN113948681B (en) | Biomass-based hard carbon compound composite material and preparation method and application thereof | |
| CN115744872B (en) | Asphalt-based soft carbon composite cellulose hard carbon negative electrode material and preparation method thereof | |
| CN114709408A (en) | Preparation method of sodium ion hard carbon negative electrode material | |
| CN111268677A (en) | Preparation method and application of novel lithium ion battery negative electrode material carbonized grape seed | |
| CN116314773A (en) | Pre-oxidized asphalt-based sodium ion battery anode material, preparation method thereof and obtained product | |
| CN111320161A (en) | Preparation method and application of asphalt-based carbon nanosheet | |
| CN116281939B (en) | Hard carbon negative electrode material of battery and preparation method thereof | |
| CN114188521B (en) | Light coating layer on surface of graphite anode material of double-ion battery and preparation method | |
| CN115385323A (en) | Heteroatom-doped biomass-derived hard carbon negative electrode material and preparation method thereof | |
| CN112599737B (en) | Sodium ion battery transition metal sulfide carbon composite negative electrode material and preparation method and application thereof | |
| CN111924843B (en) | Preparation method of cyano-modified biomass derived carbon and application of cyano-modified biomass derived carbon in potassium storage field | |
| CN110600738B (en) | Method for preparing low-temperature lithium ion battery hard carbon negative electrode material | |
| CN116364904B (en) | Preparation method of three-dimensional ordered macroporous sodium ion battery anode material | |
| CN116344779B (en) | Lithium battery composite negative electrode material and lithium battery | |
| CN116374991A (en) | Preparation method of sodium ion battery anode material based on resin precursor | |
| CN115893373A (en) | Fluorination method of coal tar pitch-based carbon material and application of sodium ion battery | |
| CN117117100A (en) | Method for preparing sodium ion battery cathode material by using yeast cell wall | |
| CN116462182A (en) | Asphalt-based nitrogen-sulfur double-doped carbon material and application thereof in sodium ion battery anode material | |
| CN116470017A (en) | Antimony triselenide/carbon fiber composite material, preparation method thereof and application thereof in potassium ion battery | |
| CN117466278A (en) | Method for ball milling modification of hard carbon material and application of ball milling modification of hard carbon material in negative electrode of sodium ion battery | |
| CN115947336A (en) | Sodium ion battery and modified hard carbon cathode thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |