CN114789998B - Negative electrode material, preparation method thereof and battery - Google Patents
Negative electrode material, preparation method thereof and battery Download PDFInfo
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- CN114789998B CN114789998B CN202111285189.XA CN202111285189A CN114789998B CN 114789998 B CN114789998 B CN 114789998B CN 202111285189 A CN202111285189 A CN 202111285189A CN 114789998 B CN114789998 B CN 114789998B
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 229910021389 graphene Inorganic materials 0.000 claims abstract description 75
- 239000011847 coal-based material Substances 0.000 claims abstract description 61
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 58
- 239000010439 graphite Substances 0.000 claims abstract description 58
- 239000011259 mixed solution Substances 0.000 claims abstract description 46
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- 239000000843 powder Substances 0.000 claims abstract description 20
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- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
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- 238000000265 homogenisation Methods 0.000 claims description 27
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- 239000010405 anode material Substances 0.000 claims description 14
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
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- 230000000630 rising effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 23
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 13
- 229910052708 sodium Inorganic materials 0.000 abstract description 13
- 239000011734 sodium Substances 0.000 abstract description 13
- 238000003860 storage Methods 0.000 abstract description 11
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- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- -1 Lithium hexafluorophosphate Chemical compound 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- 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 negative electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: mixing coal-based materials and graphite, and adding the mixture into a solvent to obtain a mixed solution A; homogenizing the mixed solution A under high pressure to obtain a mixed solution B of the coal-based material and the graphene; and (3) spray-drying the mixed solution B to obtain the composite powder of the coal-based material and the graphene. According to the negative electrode material provided by the invention, the coal-based material and graphite are used as raw materials, in the high-pressure homogenizing process, the graphite sheet is peeled off to form graphene and the coal is coated, so that the graphene composite coal-based material is finally obtained, and the coal-based material has a stable structure and excellent conductivity and sodium storage performance. The invention also provides a battery.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a negative electrode material, a preparation method thereof and a battery.
Background
The carbon material has the advantages of rich sources, environmental protection, good conductivity and the like, is successfully applied to the commercial production of lithium batteries at present, and the graphite has a long-range ordered stacking structure and good conductivity, has higher specific capacity and better cycle performance, and becomes the most common cathode material of the commercial lithium ion batteries.
The composition and working principles of lithium ion batteries and sodium ion batteries, including charge and discharge processes, are similar. Carbon materials are important negative electrode materials in lithium ion batteries and sodium ion batteries, but sodium ion batteries have limited development due to the fact that no suitable negative electrode material has been found. Successful application of carbon materials in lithium ion batteries has shown that carbon materials are one of the most promising materials for negative electrodes of sodium ion batteries. The current application of carbon materials in sodium ion batteries has the following problems:
1. the sodium ion battery cannot directly use a graphite negative electrode due to the large radius of sodium ions, the atomic radius of the sodium ions is larger than that of lithium atoms, the interlayer spacing (0.34 nm) of the graphite is limited, and the sodium ions need more energy between the intercalation graphite layers, so that the sodium storage capacity of the graphite and graphite materials is low;
2. the preparation method of the coal-based carbon material is simple, has wide application prospect in the energy storage field, but the conductivity of the coal-based carbon material is not high, and the electronic or charge conduction capability is to be improved;
3. in the application of sodium ion batteries, coal is generally calcined at high temperature to generate hard carbon, the graphitization degree of the hard carbon is small, the disorder degree is high, the interlayer spacing is large, a large number of lattice defects are generated in the internal structure, the sodium storage capacity of the sodium ion battery is derived from the fact that sodium ions are adsorbed on the lattice defects, but the structural stability of the sodium ion battery is reduced due to the large number of lattice defects in the hard carbon.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a negative electrode material and a preparation method thereof, wherein the negative electrode material takes coal-based materials and graphite as raw materials, and the preparation method of the battery negative electrode material comprises the following steps: mixing, high-pressure homogenizing, spray drying and high-temperature calcining, peeling the graphite sheet layer into graphene and coating coal in the high-pressure homogenizing process to finally obtain the graphene composite coal-based material, wherein the coal-based material has stable structure and excellent conductivity and sodium storage performance.
In a first aspect, the present invention provides a method for preparing a negative electrode material, comprising the steps of:
s1, mixing coal-based materials and graphite, and adding the mixture into a solvent to obtain a mixed solution A;
s2, homogenizing the mixed solution A under high pressure to obtain a mixed solution B of the coal-based material and the graphene;
and S3, spray drying the mixed solution B to obtain the composite powder of the coal-based material and the graphene.
Further, in the step S1, the coal-based material is obtained by subjecting coal to high temperature treatment, the coal is one or more of anthracite, coking coal and lignite, the granularity of the coal is d90 which is less than or equal to 20 μm, the carbon content of the coal is more than 90%, and the high temperature treatment satisfies the following conditions: the process is carried out in nitrogen or argon atmosphere at 400-1200 deg.c and temperature raising speed of 5-10 deg.c/min for 6-12 hr.
Further, the preparation method further comprises the step of calcining the composite powder at a high temperature.
Further, the high-temperature calcination is carried out in an inert atmosphere at a temperature of 400-1200 ℃, a heating rate of 5-10 ℃/min and a constant temperature of 6-12 hours, and the inert gas is nitrogen or argon.
Further, the mass of the graphite is 1-10% of that of the coal-based material, the graphite is one or two of expanded graphite and flake graphite, and the granularity of the graphite is D50 less than or equal to 100 mu m.
Further, the pressure of the high-pressure homogenization is 600-1200bar, and the high-pressure homogenization is finished when the homogenized granularity of the mixed liquid B reaches D90 which is less than or equal to 7 mu m. Preferably, the high pressure homogenisation is carried out at a pressure of 800-1000bar.
Further, the spray drying inlet temperature is 180-200 ℃ and the spray drying outlet temperature is 120-150 ℃. Preferably, the spray-drying inlet temperature is 190 ℃ and the outlet temperature is 130 ℃.
In a second aspect, the invention provides a negative electrode material, which is prepared by adopting the preparation method, wherein the negative electrode material is a graphene composite coal-based material, the granularity D90 of the negative electrode material is less than or equal to 7 mu m, and the mass of graphene in the negative electrode material is 1-10% of the mass of the coal-based material.
In a third aspect, the invention provides a battery comprising the negative electrode material described above, the battery comprising a sodium ion battery.
Compared with the prior art, the invention has at least the following beneficial effects:
1. the structural stability of the battery cathode material is improved. According to the invention, graphite and a coal-based material are used as raw materials, the raw materials are uniformly mixed through high-pressure homogenization, the graphite is peeled off to become graphene, the graphene is a two-dimensional material with thin sheets, under the high-pressure homogenization and spray drying process, the graphene shapes the coal-based material and coats the surface of the coal-based material, and when the coal-based carbon material is applied to a battery after subsequent high-temperature calcination, deformation or collapse caused by excessive defects is avoided, and the structural stability of the coal-based carbon material is improved.
2. The conductivity of the battery cathode material is improved. Compared with graphene prepared by a chemical method, the graphene prepared by high-pressure homogenization through a physical method has excellent electron conduction capability, and the graphene is compounded with a coal-based material, so that the conductivity of the coal-based material is improved.
3. And the sodium storage performance of the battery cathode material is improved. Sodium ions can be stored on both sides of a graphene sheet, and can be adsorbed on defect positions such as pores of a graphene material and the edges and hole positions of the graphene sheet to reversibly deintercalate sodium ions.
4. In the prepared negative electrode material, the mass ratio of the graphene is 1-10%, and the graphene not only improves the conductivity of the coal-based material, but also is used as a conductive agent, namely the negative electrode material is provided with the conductive agent, and no additional conductive agent is needed in the subsequent preparation of the battery negative electrode slurry.
Drawings
FIG. 1 is a flow chart of a method for preparing a negative electrode material according to an embodiment;
fig. 2 is a flowchart of a preparation method of a negative electrode material according to another embodiment.
Detailed Description
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
As shown in fig. 1, an embodiment provides a preparation method of a negative electrode material, which includes the following steps:
s101, mixing coal-based materials and graphite, and adding the mixture into a solvent to obtain a mixed solution A;
in this embodiment, the raw materials of the battery anode material are anthracite and expanded graphite. The pretreatment of anthracite comprises crushing and purifying. Pulverizing anthracite: placing the purchased blocky anthracite into a ball milling tank for 300r min -1 Is ground at a rotating speed of (2)Grinding until the anthracite coal is crushed until the D90 is less than or equal to 20 mu m; purification of anthracite: weighing appropriate amount of anthracite powder, adding into mixed solution of 30 wt% hydrochloric acid and 20wt% hydrofluoric acid, stirring and washing at 90deg.C for 0.5-1 hr to remove minerals in pulverized coal, vacuum filtering, removing solvent in vacuum drying oven at 80deg.C, purifying to obtain anthracite carbon content>90％。
Experiments of the inventor show that when the granularity of the anthracite is D90 less than or equal to 20 mu m, the speed of reducing the granularity of the anthracite by a high-pressure homogenizing process is faster, and the treatment time of high-pressure homogenizing of materials can be effectively reduced, so that the energy consumption cost is reduced; the graphitization process is accelerated advantageously when the high-temperature calcination is directly carried out. The impurities in the anthracite not only affect the conductivity of the material, but also prevent sodium ions from being stored, when the carbon content of the anthracite is more than 90%, the lower the impurity content in the anthracite is, the conductivity of the coal material is improved, and meanwhile, the negative electrode material prepared from the anthracite is applied to a battery, so that the occurrence of side reactions in the battery is reduced, and the rate capability of the battery is improved.
Compared with flake graphite, the expanded graphite has larger interlayer spacing and higher conductivity, and is easier to peel off and prepare graphene by a high-pressure homogenization process. When the particle size D50 of the expanded graphite is more than 100 mu m, the time for homogenizing the expanded graphite to the required particle size in a high-pressure homogenizer is long, so that the energy consumption is increased and the risk of damage to the homogenizer is increased. When the granularity D50 of the expanded graphite is less than or equal to 100 mu m, the efficiency of reducing the granularity and converting the expanded graphite into graphene in a high-pressure homogenizing process is higher, and the raw material acquisition cost is lower, so that the production and manufacturing cost is reduced, and the method is suitable for industrial production.
In the mixing of the raw materials, the mass of the expanded graphite is 1-10% of that of the anthracite, and the inventor discovers that when the addition amount of the expanded graphite is more than 10%, the high-pressure homogenizing process can not be performed due to the fact that the viscosity of mixed liquid formed by adding the raw materials into deionized water is too high in the high-pressure homogenizing process.
In both lithium batteries and sodium batteries, the amount of the conductive agent added to the negative electrode material was 10%. The mass of the expanded graphite is 1-10% of that of the anthracite, and after high-pressure homogenization treatment, the expanded graphite is converted into graphene, namely the mass of the graphene is 1-10% of that of the anthracite. In addition, the inventor discovers that the addition amount of graphene is lower than 1%, the content of graphene in the anthracite material is too small, the improvement of the conductivity of the anthracite material is not obvious, the addition amount of graphene is higher than 10%, the migration of sodium ions is influenced by the excessive amount of graphene, and the addition amount of the conductive agent has relatively no competitive advantage with the addition amount of the existing conductive agent.
S102, homogenizing the mixed solution A under high pressure to obtain a mixed solution B of the coal-based material and the graphene;
in the embodiment, anthracite and expanded graphite are mixed and added into deionized water to obtain mixed solution, and then the mixed solution is transferred into a high-pressure homogenizer for treatment. The mixing effect of the anthracite, the expanded graphite and the graphene in the liquid phase is superior to that of dry mixing of the powder, the deionized water provides a liquid environment for the anthracite and the expanded graphite so as to facilitate the dispersion of the anthracite and the expanded graphite and subsequent high-pressure homogenization, the conventional liquid phase mixing process such as stirring and the like cannot realize the effects of uniform mixing and coating among the powder, and in the high-pressure homogenization process, the materials can be uniformly mixed and the granularity is reduced due to the fact that the materials are subjected to mechanical forces such as high-speed shearing, high-frequency oscillation, cavitation, convection impact and the like. In the high-pressure homogenizing process of the mixed liquid of the anthracite and the expanded graphite, the granularity of the anthracite and the granularity of the expanded graphite are reduced, the material mixing with small granularity is more uniform, meanwhile, the lamellar layers of the expanded graphite are peeled off to obtain graphene, the surface of the anthracite can be coated by the graphene due to the thinness of the lamellar layers, the structural stability of the anthracite is improved, and the mixed liquid of the anthracite and the expanded graphite is obtained by high-pressure homogenizing.
In the high-pressure homogenizing process, the pressure is 600-1200bar, when the pressure is less than 600bar, the high-pressure homogenizing efficiency is low and the time is long, and when the pressure is more than 1200bar, the instrument is easy to damage, and when the pressure is less than 600bar or more than 1200bar, the high-pressure homogenizing pressure increases the production cost, so that the industrial production is not facilitated. After high-pressure homogenization is finished, the particle size D90 of the mixed solution of anthracite and graphene is less than or equal to 7 mu m. When D90 is more than 7 mu m, the particle size is too large to prevent the deintercalation of sodium ions and is not beneficial to the infiltration of electrolyte when the sodium ion battery is prepared subsequently. Meanwhile, the inventor finds that when the particle size D90 of the mixed solution of anthracite and graphene is less than or equal to 7 mu m, the materials in the mixed solution are uniformly dispersed, and the graphene forms a stable lamellar structure in the mixed solution, so that the stacking condition is avoided, namely, the materials in the obtained mixed solution are stable, and the wall sticking phenomenon and the material separation condition are effectively avoided in the subsequent spray drying process.
S103, spray drying the mixed solution B to obtain composite powder of the coal-based material and the graphene;
after high-pressure homogenization is finished, the mixed solution is subjected to spray drying, wherein the inlet temperature of the spray drying is 180-200 ℃, and the outlet temperature is 120-150 ℃. The solvent used in the invention is deionized water, the volatilization temperature of the deionized water is 100 ℃, and the arrangement of the inlet temperature and the outlet temperature is beneficial to accelerating the material drying efficiency while ensuring the volatilization of the solvent. The spray drying not only converts the mixed solution of graphene and coal into the graphene composite coal material powder, but also has a granulating function, so that the effect of coating the coal material with the graphene is enhanced, and the structural stability of the coal material is further enhanced.
The coal material with stable structure is obtained by spray drying, the powder leakage phenomenon caused by the superfine powder particles is avoided in the subsequent high-temperature calcination process, and the high-temperature calcination yield is improved.
And S104, calcining the composite powder at high temperature to obtain the anode material.
The calcination temperature and the heating rate during the heating process affect the interlayer spacing and the defect type and number of the prepared carbon material, and the interlayer spacing between the carbon layers can be adjusted to an optimal value suitable for deintercalation of lithium ions or sodium ions by adjusting the pyrolysis temperature. The inventor determines the high-temperature calcination parameters after multiple tests: the high-temperature calcination is carried out in inert atmosphere, the temperature is 400-1200 ℃, the temperature rising speed is 5-10 ℃/min, and the constant temperature is 6-12 hours.
In another embodiment, the preparation flow of the anode material is shown in fig. 2, and coal is processed at high temperature in inert atmosphere to obtain a coal-based material; mixing coal-based materials and graphite, and adding the mixture into a solvent to obtain a mixed solution C; homogenizing the mixed solution C under high pressure to obtain a mixed solution D of the coal-based material and the graphene; and (3) spray-drying the mixed solution D to obtain composite powder of the coal-based material and the graphene, wherein the composite powder is a negative electrode material.
The steps in the two preparation processes comprise mixing, high-pressure homogenization, spray drying and high-temperature calcination, and parameters are the same, so that the negative electrode material obtained in the two preparation processes has similar effects in the application of the sodium ion battery.
The technical scheme adopted by the invention is as follows: 1. the method comprises the steps of screening anthracite and expanded graphite, determining proportions, mixing and adding raw materials into a solvent, wherein a liquid phase provides conditions of uniform mixing and coating for the raw materials, and the selection and proportions of the raw materials ensure that the raw material mixed liquid can efficiently carry out a high-pressure homogenization process on one hand, and on the other hand, the conductivity of a negative electrode material is improved and sodium ion transmission is not hindered due to overlarge proportions in the raw materials; 2. the high-pressure homogenization is subjected to parameter adjustment according to the proportion of the raw materials, so that graphene is prepared in the high-pressure homogenization process, the graphene is coated on the coal-based material, a mixed solution which is uniformly mixed with the materials and has proper granularity is obtained, and the graphene is coated on the coal-based material, so that the conductivity and the structural stability of the coal-based material are improved; 3. according to the material after high-pressure homogenization, parameter adjustment is carried out on the spray drying process, so that the mixed solution is changed into composite powder, and the granulating function of spray drying can enhance the coating effect, thereby further improving the structural stability of the composite material; 4. the composite powder is calcined at high temperature to generate the negative electrode material, meanwhile, the graphene is tightly combined with the negative electrode, and the graphene provides sodium storage sites, so that the sodium storage performance of the coal-based material is enhanced. The cathode material has stable structure and excellent conductivity and sodium storage performance due to the synergistic effect of uniform mixing, high-pressure homogenization, spray drying and high-temperature calcination. In addition, the inventor also surprisingly found that the graphene prepared by the method not only improves the conductivity of the coal-based material, but also has the function of a conductive agent, namely the negative electrode material is provided with the conductive agent, and no additional conductive agent is needed in the subsequent preparation of the battery negative electrode slurry.
Example 1
Weighing 100g of pretreated anthracite (carbon content >90%, D90<20 μm) and 10g of expanded graphite (D50 <100 μm) in a 1L beaker, and adding 500g of deionized water to prepare a mixed solution; placing the mixed solution into a feeding cup of a high-pressure homogenizer, circularly homogenizing at a homogenizing pressure of 1000bar, sampling every other hour during homogenizing, performing particle size test on the slurry, and finishing the high-pressure homogenizing until the particle size of the slurry reaches D90<7 mu m; carrying out high-pressure homogenization to obtain composite slurry of graphene and anthracite, and carrying out spray drying on the slurry under the conditions that the inlet temperature is 190 ℃ and the outlet temperature is 130 ℃; and (3) placing the composite powder obtained by spray drying in a tube furnace, introducing inert gas nitrogen, heating to 600 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 8 hours, stopping heating, naturally cooling to normal temperature, and calcining at a high temperature to obtain the composite battery anode material of about 100g of graphene and anthracite.
Example 2
Weighing 100g of pretreated anthracite (carbon content >90%, D90<20 μm) and 1g of expanded graphite (D50 <100 μm) in a 1L beaker, and adding 500g of deionized water to prepare a mixed solution; placing the mixed solution into a feeding cup of a high-pressure homogenizer, circularly homogenizing at 800bar homogenizing pressure, sampling every other hour during homogenizing, performing particle size test on the slurry, and finishing high-pressure homogenizing until the particle size of the slurry reaches D90<5 mu m; carrying out high-pressure homogenization to obtain composite slurry of graphene and anthracite, and carrying out spray drying on the slurry under the conditions that the inlet temperature is 190 ℃ and the outlet temperature is 130 ℃; and (3) placing the composite powder obtained by spray drying in a tube furnace, introducing inert gas nitrogen, heating to 1000 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 8 hours, stopping heating, naturally cooling to normal temperature, and calcining at a high temperature to obtain the composite battery anode material of about 100g of graphene and anthracite.
Example 3
Weighing 100g of pretreated anthracite (carbon content >90%, D90<20 μm) and 6g of expanded graphite (D50 <100 μm) in a 1L beaker, and adding 500g of deionized water to prepare a mixed solution; placing the mixed solution into a feeding cup of a high-pressure homogenizer, circularly homogenizing at a homogenizing pressure of 1000bar, sampling every other hour during homogenizing, performing particle size test on the slurry, and finishing the high-pressure homogenizing until the particle size of the slurry reaches D90<7 mu m; carrying out high-pressure homogenization to obtain composite slurry of graphene and anthracite, and carrying out spray drying on the slurry under the conditions that the inlet temperature is 190 ℃ and the outlet temperature is 130 ℃; and (3) placing the composite powder obtained by spray drying in a tube furnace, introducing inert gas nitrogen, heating to 1000 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 8 hours, stopping heating, naturally cooling to normal temperature, and calcining at a high temperature to obtain the composite battery anode material of about 100g of graphene and anthracite.
Example 4
Weighing 100g of pretreated anthracite (carbon content is more than 90%, D90 is less than 20 mu m), placing the anthracite in a tube furnace, introducing inert gas nitrogen, heating to 600 ℃ at a heating speed of 5 ℃/min, keeping the temperature for 8 hours, stopping heating, and naturally cooling to normal temperature to obtain about 100g of coal-based material; weighing 100g of coal-based material subjected to high-temperature calcination and 10g of expanded graphite (D50 <100 mu m) and adding the mixture into 500g of deionized water to prepare a mixed solution; placing the mixed solution into a feeding cup of a high-pressure homogenizer, circularly homogenizing at a homogenizing pressure of 1000bar, sampling every other hour during homogenizing, performing particle size test on the slurry, and finishing the high-pressure homogenizing until the particle size of the slurry reaches D90<7 mu m; and (3) carrying out high-pressure homogenization to obtain composite slurry of graphene and coal-based materials, and carrying out spray drying on the slurry under the conditions that the inlet temperature is 190 ℃ and the outlet temperature is 130 ℃ to obtain the composite battery anode material of graphene and anthracite.
Example 5
Weighing 100g of pretreated anthracite (carbon content is more than 90%, D90 is less than 20 mu m), placing the anthracite in a tube furnace, introducing inert gas nitrogen, heating to 1000 ℃ at a heating speed of 5 ℃/min, keeping the temperature for 8 hours, stopping heating, and naturally cooling to normal temperature to obtain about 100g of coal-based material; weighing 100g of coal-based material subjected to high-temperature calcination and 1g of expanded graphite (D50 <100 mu m) and adding the coal-based material and the expanded graphite into 500g of deionized water to prepare a mixed solution; placing the mixed solution into a feeding cup of a high-pressure homogenizer, circularly homogenizing at 800bar homogenizing pressure, sampling every other hour during homogenizing, performing particle size test on the slurry, and finishing high-pressure homogenizing until the particle size of the slurry reaches D90<5 mu m; and (3) carrying out high-pressure homogenization to obtain composite slurry of graphene and coal-based materials, and carrying out spray drying on the slurry under the conditions that the inlet temperature is 190 ℃ and the outlet temperature is 130 ℃ to obtain the composite battery anode material of graphene and anthracite.
Example 6
Weighing 100g of pretreated anthracite (carbon content is more than 90%, D90 is less than 20 mu m), placing the anthracite in a tube furnace, introducing inert gas nitrogen, heating to 1000 ℃ at a heating speed of 5 ℃/min, keeping the temperature for 8 hours, stopping heating, and naturally cooling to normal temperature to obtain about 100g of coal-based material; weighing 100g of coal-based material subjected to high-temperature calcination and 6g of expanded graphite (D50 <100 mu m) and adding the coal-based material and the expanded graphite into 500g of deionized water to prepare a mixed solution; placing the mixed solution into a feeding cup of a high-pressure homogenizer, circularly homogenizing at a homogenizing pressure of 1000bar, sampling every other hour during homogenizing, performing particle size test on the slurry, and finishing the high-pressure homogenizing until the particle size of the slurry reaches D90<7 mu m; and (3) carrying out high-pressure homogenization to obtain composite slurry of graphene and coal-based materials, and carrying out spray drying on the slurry under the conditions that the inlet temperature is 190 ℃ and the outlet temperature is 130 ℃ to obtain the composite battery anode material of graphene and anthracite.
Comparative example 1
This example differs from example 3 in that no expanded graphite is added and other parameters and conditions are exactly the same as example 3.
Comparative example 2
This example differs from example 6 in that no expanded graphite is added and other parameters and conditions are exactly the same as example 6.
The cathode materials in the examples and the comparative examples are respectively mixed with polyvinylidene fluoride according to the mass ratio of 9:1, deionized water is added and uniformly stirred to prepare slurry, the prepared slurry is coated on a copper foil current collector through a coating machine, and the copper foil coated with the slurry is dried in a vacuum drying oven at 100 ℃ for 12 hoursAfter the drying, the electrode sheet was cut into a wafer having a diameter of 12mm by a microtome. Glass fiber membrane is used as diaphragm, 1mol L -1 Lithium hexafluorophosphate was dissolved in 1L of a mixed solution of ethylene carbonate and dimethyl carbonate (volume ratio 1:1) as an electrolyte, and a CR2025 button cell was assembled in a glove box under an argon atmosphere. The electrochemical performance of the battery is tested on a Land 2001A type battery test system, a metal sodium sheet is used as a counter electrode, and the charge-discharge voltage range is 0.01-3V. Constant current charge and discharge tests were performed at a current density of 0.1C, and the CR2025 coin cell test data for the assembly of the negative electrode materials in the examples are shown in table 1.
Table 1 electrochemical properties of different anode materials in examples
As is clear from Table 1, when the addition amount of graphite was 6% of the mass of anthracite, that is, the mass ratio of graphene in the coal-based material was 6%, the electrochemical performance of the anode material was optimal, and in example 3, the reversible specific capacity was 237mAh g -1 The initial coulombic efficiency was 75%, the capacity retention after 50 weeks of cycling was 92.7%, and the reversible specific capacity was 240mAh g in example 6 -1 The first coulombic efficiency was 74% and the capacity retention after 50 weeks of cycling was 94.5%. The electrochemical properties of the anode materials in examples 1 to 6 are superior to those of comparative examples 1 and 2.
The graphene material has a unique sodium storage mechanism, and sodium ions can be stored on both sides of the graphene sheet and can be adsorbed on defect positions such as pores of the graphene material and the edges and hole positions of the graphene sheet to reversibly deintercalate sodium ions. According to the invention, the added graphite is subjected to high-pressure homogenization stripping to form graphene, and the graphene and the coal-based material are compounded to obtain the negative electrode material, so that the sodium storage point is increased, and the situation that single-layer graphene is easily subjected to secondary stacking in the charging and discharging process to cause loss of the sodium storage point is avoided; graphene is a two-dimensional material with a thin sheet layer, can be adsorbed on the surface of a coal-based material for coating in the high-pressure homogenizing and spray drying process, and can be used for adjusting the structure of the coal-based material to realize the shaping of the coal-based material; compared with a single coal-based material, the negative electrode material provided by the invention has higher negative electrode capacity, more stable structure and high capacity retention rate after 50 weeks of circulation.
Four-probe method for testing electron conductivity of anode material: mixing the cathode material and polyvinylidene fluoride according to the mass ratio of 9:1, adding N methyl pyrrolidone, stirring uniformly to prepare slurry, coating the prepared slurry on a PET film through a coating machine, drying the PET film coated with the slurry in a vacuum drying oven at 100 ℃ for 4 hours, taking out, and cutting a small wafer with the diameter of 19mm by a microtome. Film resistivity tests were performed on a ST2258C multifunctional digital four-probe tester. The test data are shown in Table 2.
Table 2 film resistivity of pole pieces made from different materials in examples
As can be seen from the data in table 2, in both the processes, when the mass ratio of graphene in the coal-based material is 6%,10%, the resistivity of the negative electrode material is the lowest, the conductivity is better, and the difference is not large, indicating that a good conductive network has been achieved at a ratio of 6%, so that the graphene is preferably 6% based on the cost consideration, and the conductivity of the negative electrode materials in examples 1 to 6 is better than that of comparative examples 1 and 2. The graphene is compounded with the coal-based material, so that the conductivity of the coal-based material is improved.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (4)
1. A method for preparing a negative electrode material, comprising the steps of:
s1, mixing a coal-based material and graphite, and then adding the mixture into a solvent to obtain a mixed solution A, wherein the mass of the graphite is 1-10% of that of the coal-based material, the graphite is one or two of expanded graphite and flake graphite, and the granularity of the graphite is D50 less than or equal to 100 mu m;
s2, homogenizing the mixed solution A under high pressure to obtain mixed solution B of the coal-based material and the graphene, wherein the pressure of the high pressure homogenization is 600-1200bar, and the high pressure homogenization is finished when the homogenized granularity of the mixed solution B reaches D90 which is less than or equal to 7 mu m;
s3, spray drying the mixed solution B to obtain composite powder of the coal-based material and the graphene, and calcining the composite powder at high temperature;
in the step S1, the coal-based material is obtained by high-temperature treatment of coal, wherein the coal is one or more of anthracite, coking coal and lignite, the granularity of the coal is D90 less than or equal to 20 mu m, the carbon content of the coal is more than 90%, and the high-temperature treatment meets the following conditions: the method is carried out in nitrogen or argon atmosphere at 400-1200 ℃ and at a temperature rising speed of 5-10 ℃/min for 6-12 hours;
the inlet temperature of the spray drying is 180-200 ℃ and the outlet temperature is 120-150 ℃; the high-temperature calcination is carried out in an inert atmosphere at a temperature of 400-1200 ℃, a heating speed of 5-10 ℃/min and a constant temperature of 6-12 hours, and the inert gas is nitrogen or argon.
2. The negative electrode material is characterized by being prepared by the preparation method of claim 1, wherein the negative electrode material is a graphene composite coal-based material, the granularity D90 of the negative electrode material is less than or equal to 7 mu m, and the mass of the graphene in the negative electrode material is 1-10% of the mass of the coal-based material.
3. A battery comprising the anode material according to claim 2.
4. The battery of claim 3, wherein the battery comprises a sodium ion battery.
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