CN113735095A - Porous hard carbon material and preparation method and application thereof - Google Patents
Porous hard carbon material and preparation method and application thereof Download PDFInfo
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- CN113735095A CN113735095A CN202110902423.2A CN202110902423A CN113735095A CN 113735095 A CN113735095 A CN 113735095A CN 202110902423 A CN202110902423 A CN 202110902423A CN 113735095 A CN113735095 A CN 113735095A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 92
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 7
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- 238000000034 method Methods 0.000 claims description 21
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- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
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- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
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- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
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- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
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- 239000010405 anode material Substances 0.000 description 1
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- 239000003273 ketjen black Substances 0.000 description 1
- GBCAVSYHPPARHX-UHFFFAOYSA-M n'-cyclohexyl-n-[2-(4-methylmorpholin-4-ium-4-yl)ethyl]methanediimine;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1CCCCC1N=C=NCC[N+]1(C)CCOCC1 GBCAVSYHPPARHX-UHFFFAOYSA-M 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
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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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of battery materials, and particularly discloses a porous hard carbon material, and a preparation method and application thereof. The porous hard carbon material provided by the invention is a honeycomb-shaped porous material, and the interior of the porous hard carbon material is provided with a three-stage porous structure of nano macropores, mesopores and micropores; preparing a solid precursor by mixing a carbon source and a template agent; then, carrying out high-temperature heat treatment on the solid precursor in an inert gas atmosphere, and carrying out primary pore-forming; and then crushing the heat-treated material into powder, and carrying out acid washing for secondary pore forming to obtain the porous hard carbon material. The hard carbon material prepared by the invention has large interlayer spacing and rich three-level nano porous structures, and provides more channels for the transmission of lithium ions or sodium ions; meanwhile, more active sites and lithium or sodium storage spaces are provided for ion insertion and extraction, and the secondary battery made of the hard carbon material has high capacity and stable cycle performance.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a negative electrode material for a secondary battery, and specifically relates to a porous hard carbon material, and a preparation method and application thereof.
Background
Currently, the negative electrode material of Lithium Ion Batteries (LIBs) in commercial use is mainly graphite material, and graphite stores electric quantity by means of intercalation/deintercalation of lithium ions in a long-range ordered carbon layer. With the gradual maturity of lithium ion battery technology and the explosive increase of demand, the consumption of lithium materials is continuously increased, which leads to the sharp rise of lithium price, and it is very important to find an economic and efficient alternative solution for lithium ion batteries. Na (Na)+With Li+Similar physicochemical properties, abundant reserves and low cost, so that Sodium Ion Batteries (SIB) are receiving wide attention. However, the interlayer spacing of graphite is not sufficient to make the radius of Na larger+Free intercalation between the layers, and therefore, researchers have been very challenging in finding suitable anode materials.
In addition, the capacity of the secondary battery using the graphite material as the negative electrode material is insufficient, the requirement of the power battery is not met, the stability of the layered structure needs to be improved, and the rate capability is not good enough.
Compared with graphite, the hard carbon has the structural characteristics of short-range order and isotropy, has larger interlayer spacing, can meet the requirement of free deintercalation of sodium ions between layers, and can also accelerate the diffusion of lithium ions; meanwhile, the hard carbon material also has the characteristics of good cycle performance and rate capability, low cost and the like. Therefore, the hard carbon negative electrode material can show higher capacity in secondary batteries including lithium ion batteries and sodium ion batteries, and has higher application potential.
There is currently research on the preparation of hard carbon materials. The present invention aims to provide a new porous hard carbon material and a preparation method thereof, so as to reduce the production cost and improve the performance of the hard carbon material.
Disclosure of Invention
The invention mainly solves the technical problem of providing a novel porous hard carbon material which can be used as a negative electrode material of a secondary battery comprising a lithium ion battery and a sodium ion battery, in particular to a negative electrode material of the sodium ion battery.
The invention also provides a preparation method of the novel porous hard carbon material.
The invention also provides application of the novel porous hard carbon material as a negative electrode material of a secondary battery.
In order to solve the above technical problems, in a first aspect, the present invention provides a method for preparing a porous hard carbon material, comprising the steps of:
(1) mixing a carbon source and a template agent to prepare a solid precursor;
the carbon source is at least one of high molecular polymer, petrochemical products and biomass materials;
preferably, the high molecular polymer is at least one selected from polyacrylonitrile, phenolic resin, epoxy resin, polyethylene terephthalate and polyfurfuryl alcohol;
the petrochemical product is at least one selected from natural asphalt, coal-based asphalt, petroleum-based asphalt and oxidized asphalt;
the biomass material is any one or more of glucose, starch, sucrose, cellulose, lignin, amino acid and plant residues; for example, the biomass material can also be any one or more of pinecone, coconut, walnut shell, wheat straw, rice hull, blue algae, bean dregs, banana peel, cotton, peat, seaweed and cotton shell;
the template agent is high-melting-point insoluble carbonate; preferably, the template is at least one selected from calcium carbonate, manganese carbonate, magnesium carbonate and zinc carbonate;
(2) carrying out heat treatment on the solid precursor obtained in the step (1) in an inert gas atmosphere, and carrying out primary pore-forming;
preferably, the equipment used for the heat treatment in step (2) can be a tube furnace;
preferably, inert gas is introduced into the tube furnace for protection, high-temperature heat treatment is carried out to crack and carbonize the material, and the template agent is decomposed at high temperature to release CO2Carrying out primary pore forming;
preferably, the inert gas can be at least one of nitrogen, argon and nitrogen-argon mixed gas;
preferably, the heat treatment temperature adopted by the heat treatment is 1000-1800 ℃, further preferably 1100-1700 ℃, and more preferably 1200-1500 ℃;
preferably, the heating rate for the heat treatment is 0.5-10 ℃/min, more preferably 1-6 ℃/min, and even more preferably 2-5 ℃/min;
preferably, the time of the heat treatment is 1-10 h, more preferably 2-8 h, and even more preferably 2-5 h;
(3) and (3) crushing the material treated in the step (2) into powder, and carrying out acid washing to carry out secondary pore forming to obtain the porous hard carbon material.
In the step (3), removing the residual template agent oxide in the material by acid washing to realize secondary pore-forming; when the template agent carbonate is used for primary pore forming, the template agent carbonate is decomposed at high temperature to release CO2Then forming oxides, continuously taking the residual oxides as a template agent, decomposing and removing the oxides by acid washing in the step (3), and carrying out secondary pore-forming; and after the template agent oxide is completely washed by acid, washing with water until the hard carbon is pure, thus obtaining the porous hard carbon material.
As a preferred embodiment of the present invention, when the solid precursor is prepared in step (1), the carbon source may be heated to be softened, and then mixed with the template agent uniformly, cooled and hardened to prepare the solid precursor.
As a preferred embodiment of the present invention, when the solid precursor is prepared in step (1), a solvent for dissolving a carbon source may be further added.
Preferably, the carbon source, the template and the solvent are mixed, stirred uniformly and then dried to prepare the solid precursor.
Preferably, the solvent for dissolving the carbon source may be water or DMF, etc.
As a preferred embodiment of the present invention, when preparing the solid precursor, the mass ratio of the carbon source to the template is 100: (1-30). More preferably 100: (10-30).
In a preferred embodiment of the present invention, the acid used in the acid washing in step (3) is any acid capable of removing the template agent oxide, and is preferably at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and oxalic acid.
Preferably, after the acid-washing secondary pore-forming, water washing is carried out to obtain the porous hard carbon material.
In a second aspect, the present invention provides a porous hard carbon material, which is a honeycomb-shaped porous hard carbon material having a three-stage porous structure including nano-macropores, mesopores and micropores.
The particle size of the porous hard carbon material is 1-200 mu m, the diameter of the nano macroporous structure is 50-500 nm, the diameter of the mesoporous structure is 2-50 nm, and the diameter of the microporous structure is less than or equal to 2 nm.
The macroscopic morphology of the porous hard carbon material is in an irregular honeycomb block-shaped porous structure.
In a preferred embodiment of the present invention, the particle size of the porous hard carbon material is 1 to 50 μm, and more preferably 1 to 10 μm.
Preferably, the diameter of the nano macroporous structure is 50-200 nm.
Preferably, the diameter of the mesoporous structure is 2-30 nm.
As a preferred embodiment of the present invention, the porous hard carbon material contains a doping element comprising one or more of N, B, P and S. The doping elements are mainly introduced from different carbon sources.
The invention also provides the porous hard carbon material prepared by the preparation method of the first aspect.
In a third aspect, the present invention provides a method of preparing a negative electrode sheet for a secondary battery, the method comprising the steps of:
(1) preparing the porous hard carbon material by using the porous hard carbon material of the second aspect or the method of the first aspect; and
(2) and (2) mixing the porous hard carbon material prepared in the step (1) with a conductive agent and a binder in proportion in the presence of a solvent to prepare the negative plate of the secondary battery.
Preferably, in the step (2), after the porous hard carbon material, the conductive agent and the binder are mixed in proportion in the presence of the solvent, the negative electrode sheet of the secondary battery is prepared through the steps of homogenizing, coating, drying and cutting.
Preferably, the negative plate is baked in a vacuum oven at 100 ℃ to remove trace water.
Preferably, the conductive agent is at least one of carbon black, acetylene black, ketjen black, vapor-deposited carbon fiber, conductive graphite, carbon nanotube, graphene, and the like.
In a fourth aspect, the present invention provides a negative electrode sheet for a secondary battery produced by the production method of the third aspect.
In a fifth aspect, the present invention provides a method of manufacturing a secondary battery, the method comprising the steps of:
(1) preparing the porous hard carbon material by using the porous hard carbon material of the second aspect or the method of the first aspect; and
(2) and (2) mixing the porous hard carbon material prepared in the step (1) with a conductive agent and a binder in proportion in the presence of a solvent to prepare the negative plate of the secondary battery.
Preferably, there is provided a method of manufacturing a lithium ion battery, the method comprising the steps of:
(1) preparing the porous hard carbon material by using the porous hard carbon material of the second aspect or the method of the first aspect; and
(2) mixing the porous hard carbon material prepared in the step (1) with a conductive agent and a binder in proportion in the presence of a solvent to prepare a negative plate of a lithium ion battery;
wherein the binder is at least one of polyacrylic acid, lithium polyacrylate, CMC/SBR and the like;
LiPF with electrolyte of 1mol/L6A solution;
the solvent consists of EC (ethylene carbonate) and DEC (diethyl carbonate) in a volume ratio of 1: 1.
Preferably, there is provided a method of making a sodium ion battery, the method comprising the steps of:
(1) preparing the porous hard carbon material by using the porous hard carbon material of the second aspect or the method of the first aspect; and
(2) mixing the porous hard carbon material prepared in the step (1), a conductive agent and a binder in proportion in the presence of a solvent to prepare a negative plate of the sodium-ion battery;
wherein the binder is at least one of sodium alginate, sodium polyacrylate, CMC/SBR and the like;
electrolyte is 1mol/L NaPF6A solution;
the solvent consisted of EC (ethylene carbonate) and DEC (diethyl carbonate) in a volume ratio of 1: 1.
In a sixth aspect, the present invention provides a secondary battery having the negative electrode sheet produced by the production method of the fourth aspect, or a secondary battery produced by the method of the fifth aspect.
The secondary battery is a lithium ion battery or a sodium ion battery.
In some embodiments, the battery is a CR2032 type coin cell battery.
In a seventh aspect, the present invention provides the use of the hard carbon material of the second aspect or the hard carbon material prepared by the method of the first aspect as a negative electrode material of a secondary battery, or in the preparation of a secondary battery.
The invention uses carbonate as a template agent, and CO is released through the decomposition of the carbonate in the process of preparing hard carbon at high temperature2A first pore-forming is performed followed by a second pore-forming by acid-washing to remove the remaining template oxide. The prepared hard carbon material has large interlayer spacing and rich three-level nano porous structures through two pore forming, namely, the porous hard carbon material has three-level porous structures of nano macropores, mesopores and micropores, so that the infiltration of electrolyte is facilitated, and more channels are provided for the transmission of lithium ions or sodium ions; meanwhile, more active sites and lithium or sodium storage spaces are provided for ion intercalation and deintercalation, so that the secondary battery made of the hard carbon material provided by the invention has high capacity and stable cycle performance.
The method can also controllably adjust the size and the amount of the pore structure of the prepared hard carbon material by adjusting the size and the dosage of the adopted template agent, thereby realizing the regulation and the control of gram volume and first effect exerted by the hard carbon material.
Drawings
FIG. 1 is a schematic structural view of a porous hard carbon material provided by the present invention;
fig. 2 is an SEM image of a porous hard carbon material provided in example 2 of the present invention;
FIG. 3 is a graph of the charge and discharge performance of a lithium ion battery assembled using the porous hard carbon materials prepared in examples 2-5 of the present invention;
fig. 4 is a graph showing the charge and discharge performance of a sodium ion battery assembled by using the porous hard carbon materials prepared in examples 2 to 5 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples.
Example 1
The embodiment provides a porous hard carbon material, a schematic structural diagram of which is shown in fig. 1, and an SEM image of which is shown in fig. 2, and it can be seen that the porous hard carbon material is a honeycomb-shaped porous material with an irregular block-shaped macro morphology, and the porous hard carbon material has a three-stage porous structure of nano macropores, mesopores and micropores inside.
The particle size of the porous hard carbon material is 1-50 mu m, the diameter of the nano macroporous structure is 50-200 nm, the diameter of the mesoporous structure is 2-30 nm, and the diameter of the microporous structure is less than or equal to 2 nm.
Example 2
The embodiment provides a porous hard carbon material which is prepared by the following steps: dissolving 100g of starch in sufficient hot water, then adding 10g of magnesium carbonate, uniformly stirring, and drying in a forced air drying oven at 100 ℃ to obtain a solid precursor;
putting the solid precursor into a tube furnace, introducing nitrogen for protection, heating to 1500 ℃ at the speed of 5 ℃/min, keeping the temperature for 5 hours, carrying out primary pore forming, and then naturally cooling;
and mechanically crushing the naturally cooled carbonized material into powder, adding sufficient dilute sulfuric acid, stirring for 2 hours, carrying out acid washing for secondary pore forming, washing, carrying out suction filtration until the material is neutral, and drying to obtain the porous hard carbon material, which is recorded as PHC-1.
As shown in the SEM image of the porous hard carbon material in figure 2, rich porous structures can be observed from the SEM image, and pore structures with different pore size distributions can be observed at the same time, which shows that the method has obvious pore-forming effect and prepares the porous hard carbon material with the multi-level pore gradient.
Example 3
The embodiment provides a porous hard carbon material which is prepared by the following steps: dissolving 100g of polyacrylonitrile in sufficient DMF solvent, adding 1g of calcium carbonate, uniformly stirring, and drying in a 150 ℃ forced air drying oven to obtain a solid precursor;
putting the solid precursor into a tube furnace, introducing argon for protection, heating to 1300 ℃ at the speed of 3 ℃/min, keeping the temperature for 3 hours, carrying out primary pore forming, and then naturally cooling;
and mechanically crushing the naturally cooled carbonized material into powder, adding sufficient dilute hydrochloric acid, stirring for 2 hours, carrying out acid washing for secondary pore forming, then washing, carrying out suction filtration until the material is neutral, and drying to obtain the porous hard carbon material, which is recorded as PHC-2.
Example 4
The embodiment provides a porous hard carbon material which is prepared by the following steps: dissolving 100g of sucrose in sufficient water, adding 20g of calcium carbonate, uniformly stirring, and then drying in a forced air drying oven at 100 ℃ to obtain a solid precursor;
putting the solid precursor into a tube furnace, introducing nitrogen for protection, heating to 1400 ℃ at the speed of 2 ℃/min, keeping the temperature for 4 hours, carrying out primary pore forming, and then naturally cooling;
and mechanically crushing the naturally cooled carbonized material into powder, adding sufficient dilute hydrochloric acid, stirring for 2 hours, carrying out acid washing for secondary pore forming, then washing, carrying out suction filtration until the material is neutral, and drying to obtain the porous hard carbon material, which is recorded as PHC-3.
Example 5
The embodiment provides a porous hard carbon material which is prepared by the following steps: heating 100g of oxidized asphalt until the oxidized asphalt is completely softened, then adding 15g of calcium carbonate, stirring and mixing uniformly, and cooling and hardening to obtain a solid precursor;
putting the solid precursor into a tube furnace, introducing argon for protection, heating to 1500 ℃ at the speed of 5 ℃/min, keeping the temperature for 5 hours, carrying out primary pore forming, and then naturally cooling;
and mechanically crushing the naturally cooled carbonized material into powder, adding sufficient dilute hydrochloric acid, stirring for 2 hours, carrying out acid washing for secondary pore forming, then washing, carrying out suction filtration until the material is neutral, and drying to obtain the porous hard carbon material, which is recorded as PHC-4.
Example 6
In this example, the porous hard carbon materials prepared in examples 2 to 5 were used as active materials, and were assembled into a button lithium ion battery and a sodium ion battery, respectively, and material performance tests were performed.
The method comprises the following specific steps:
(1) battery assembly
Respectively taking one of PHC-1, PHC-2, PHC-3 and PHC-4 as an active material, matching conductive carbon black and CMC/SBR according to the proportion of 8:1:1, and performing homogenate, coating, drying and cutting to prepare an electrode slice;
the lithium metal sheet is taken as a negative electrode, and 1mol/L LiPF is adopted as electrolyte6The solvent is EC (ethylene carbonate) and DEC (diethyl carbonate) in a volume ratio of 1:1) The mixture is assembled into a CR2032 type button lithium ion battery;
sodium metal sheet is taken as a negative electrode, and 1mol/L NaPF is adopted as electrolyte6The solution and the solvent are a mixture of EC (ethylene carbonate) and DEC (diethyl carbonate) in a volume ratio of 1:1, and the CR2032 button sodium-ion battery is assembled.
(2) Performance testing
The assembled lithium ion battery and sodium ion battery are respectively tested by adopting the following test conditions;
the test conditions were: and (3) carrying out constant-current charge and discharge circulation at 0.1C multiplying power, wherein the voltage range is 0.005-2.0V, and standing for 5 min.
The charge and discharge performance test results of the lithium ion battery are shown in the following table 1, and the charge and discharge performance graph is shown in fig. 3.
TABLE 1
As can be seen from Table 1, the first discharge gram capacity of the lithium ion battery prepared by the invention can reach more than 360mAh/g, and especially the first discharge gram capacity of 534mAh/g can be reached by taking sucrose as a biomass material; the first charge gram capacity can reach more than 310mAh/g, and particularly, the first charge gram capacity of 401mAh/g can be reached by taking sucrose as a biomass material; the coulombic efficiency of the first circle can reach more than 75 percent, and the lithium ion battery prepared by the invention has higher capacity and better energy density.
The charge and discharge performance test results of the sodium ion battery are shown in the following table 2, and the charge and discharge performance graph is shown in fig. 4.
TABLE 2
As can be seen from Table 2, the first discharge gram capacity of the sodium-ion battery prepared by the invention can reach more than 343mAh/g, and especially the first discharge gram capacity of 585mAh/g can be reached by taking sucrose as a biomass material; the first charge gram capacity can reach more than 296mAh/g, and particularly, the first charge gram capacity of 361mAh/g can be reached by taking cane sugar as a biomass material; the first-turn coulombic efficiency can reach more than 62%, and the sodium ion battery prepared by the method has higher capacity and better energy density.
As can be seen from tables 1 and 2, when the hard carbon material is prepared, the more the template agent is added, the richer the porous structure of the finally obtained hard carbon material is, the larger the electrolyte contact surface is, the more the lithium or sodium active sites are embedded, and the higher the gram capacity exerted by the hard carbon material is; meanwhile, the larger the contact surface is, the more active lithium or sodium is lost when an SEI film is formed in the process of first charge and discharge, so that the coulombic efficiency of the first circle is lower. Therefore, when the hard carbon material is prepared, the size and the amount of the pore structure of the prepared hard carbon material can be controllably adjusted by adjusting the using amount and/or the scale of the template agent, so that the gram volume and the first effect of the hard carbon material are regulated and controlled.
In addition, it should be noted that, since the radius of sodium ions is larger than that of lithium ions, the difficulty of sodium ion intercalation is greater than that of lithium ions, and therefore, the gram capacity exhibited by the same kind of hard carbon material in a sodium ion battery system is lower than that exhibited by a lithium ion battery system under the same conditions.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a porous hard carbon material is characterized by comprising the following steps:
(1) mixing a carbon source and a template agent to prepare a solid precursor;
the carbon source is at least one of high molecular polymer, petrochemical products and biomass materials;
preferably, the high molecular polymer is at least one selected from polyacrylonitrile, phenolic resin, epoxy resin, polyethylene terephthalate and polyfurfuryl alcohol;
the petrochemical product is at least one selected from natural asphalt, coal-based asphalt, petroleum-based asphalt and oxidized asphalt;
the biomass material is any one or more of glucose, starch, sucrose, cellulose, lignin, amino acid and plant residues;
the template agent is high-melting-point insoluble carbonate; preferably, the template is at least one selected from calcium carbonate, manganese carbonate, magnesium carbonate and zinc carbonate;
(2) carrying out heat treatment on the solid precursor obtained in the step (1) in an inert gas atmosphere, and carrying out primary pore-forming;
(3) and (3) crushing the material treated in the step (2) into powder, and carrying out acid washing to carry out secondary pore forming to obtain the porous hard carbon material.
2. The preparation method according to claim 1, wherein the mass ratio of the carbon source to the template in the step (1) is 100: (1-30).
3. The method according to claim 1 or 2, wherein the temperature of the heat treatment in the step (2) is 1000 to 1800 ℃;
preferably, the heating rate of the heat treatment is 0.5-10 ℃/min; and/or the time of the heat treatment is 1-10 h.
4. The method according to claim 3, wherein the acid washing in the step (3) is performed by using at least one acid selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and oxalic acid.
5. The method according to any one of claims 1 to 4, wherein a solvent for dissolving a carbon source is further added when the solid precursor is prepared in step (1).
6. A porous hard carbon material is characterized in that the porous hard carbon material is a honeycomb-shaped porous hard carbon material, and the interior of the porous hard carbon material is provided with a three-stage porous structure which comprises a nano macroporous structure, a mesoporous structure and a microporous structure;
the particle size of the porous hard carbon material is 1-200 mu m, the diameter of the nano macroporous structure is 50-500 nm, the diameter of the mesoporous structure is 2-50 nm, and the diameter of the microporous structure is less than or equal to 2 nm;
preferably, the porous hard carbon material is prepared by the preparation method of any one of claims 1 to 5.
7. Use of the porous hard carbon material prepared by the preparation method of any one of claims 1 to 5 or the porous hard carbon material of claim 6 in preparation of a secondary battery, preferably as a secondary battery negative electrode material.
8. A negative electrode sheet for a secondary battery, which is made of the porous hard carbon material prepared by the preparation method of any one of claims 1 to 5 or the porous hard carbon material of claim 6.
9. A preparation method of a secondary battery negative plate is characterized by comprising the following steps:
(1) a porous hard carbon material produced by the production method according to any one of claims 1 to 5 or the porous hard carbon material according to claim 6; and
(2) and (2) mixing the porous hard carbon material prepared in the step (1) with a conductive agent and a binder in proportion in the presence of a solvent to prepare the negative plate of the secondary battery.
10. A secondary battery characterized by comprising the negative electrode sheet of claim 8 or the negative electrode sheet obtained by the production method of claim 9; preferably, the secondary battery is a lithium ion battery or a sodium ion battery.
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