CN112467116A - Graphite coating material, preparation method thereof and battery cathode - Google Patents
Graphite coating material, preparation method thereof and battery cathode Download PDFInfo
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- CN112467116A CN112467116A CN202011383817.3A CN202011383817A CN112467116A CN 112467116 A CN112467116 A CN 112467116A CN 202011383817 A CN202011383817 A CN 202011383817A CN 112467116 A CN112467116 A CN 112467116A
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- H01M4/02—Electrodes composed of, or comprising, active material
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- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y02E60/10—Energy storage using batteries
Abstract
The application relates to the field of materials, in particular to a graphite coating material, a preparation method thereof and a battery cathode. The graphite coating material comprises: an inner core comprising graphite; and the shell is coated outside the inner core and comprises tantalum-doped lithium lanthanum zirconium oxide, amorphous carbon and a conductive material. The surface coating layer of the graphite is doped with tantalum-doped lithium lanthanum zirconium oxygen and a conductive material, so that the transmission rate and the diffusion coefficient of lithium ions can be effectively improved, and the electronic conductivity of the material can be effectively improved by the conductive material; the tantalum-doped lithium lanthanum zirconium oxide, the amorphous carbon and the conductive material in the shell cooperatively show good lithium ion conductivity and electronic conductivity, so that the ion transmission rate and the conductivity of the graphite coating material are favorably improved, and the multiplying power performance, the safety performance and the cycle performance of the graphite cathode material can be effectively improved.
Description
Technical Field
The application relates to the field of materials, in particular to a graphite coating material, a preparation method thereof and a battery cathode.
Background
At present, the negative electrode material of the lithium ion battery mainly comprises artificial graphite, and has the defects of poor rate capability, safety performance deviation in the application process and the like; the rate of lithium ion intercalation/deintercalation of the material can be improved by coating soft carbon or hard carbon on the surface of the artificial graphite, but in the process of charging and discharging, lithium ion intercalation needs to enter and exit from the interlayer of the graphite, the path is longer, the diffusion coefficient of the lithium ion is lower, the ion transmission rate is slower, and the rate performance of the material is limited.
Disclosure of Invention
An object of an embodiment of the present application is to provide a graphite coating material, which aims to improve rate capability of a graphite negative electrode material.
A first aspect of the present application provides a graphite clad material, comprising:
an inner core comprising graphite; and
and the shell is coated outside the inner core and comprises tantalum-doped lithium lanthanum zirconium oxide, amorphous carbon and a conductive material.
Tantalum-doped lithium lanthanum zirconium oxide and a conductive material are doped in the surface coating layer of the graphite, so that the transmission rate and the diffusion coefficient of lithium ions can be effectively improved, and the electronic conductivity of the graphite can be effectively improved by the tantalum-doped lithium lanthanum zirconium oxide; the tantalum-doped lithium lanthanum zirconium oxide, the amorphous carbon and the conductive material in the shell cooperatively show good lithium ion conductivity and electronic conductivity, so that the ion transmission rate and the conductivity of the graphite coating material are favorably improved, and the multiplying power performance, the safety performance and the cycle performance of the graphite cathode material can be effectively improved.
In some embodiments of the first aspect of the present application, the tantalum-doped lithium lanthanum zirconium oxide comprises 1% to 10% of the total mass of the housing;
optionally, the tantalum-doped lithium lanthanum zirconium oxide accounts for 4% -8% of the total mass of the shell;
optionally, the shell has a thickness of 2nm to 200 nm.
The thickness of the shell is 2nm-200nm, and if the particle size is too small, the cost is high; if the particle size is too large, the outer shell has poor graphite coating performance and is easy to peel off from the graphite inner shell.
In some embodiments of the first aspect of the present application, the mass ratio of tantalum-doped lithium lanthanum zirconium oxide to the graphite is (0.5-5): 100, respectively;
optionally, the mass ratio of the tantalum-doped lithium lanthanum zirconium oxide to the graphite is (1-3): 100, respectively;
optionally, the mass ratio of the doped lithium lanthanum zirconium oxygen to the conductive material is (1-10): (0.2-2).
In a second aspect, the present application provides a method for preparing a graphite coating material, including:
mixing lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate, tantalum pentoxide, an oxidation conductive material and water, carrying out hydrothermal reaction for 1-12 h at 100-200 ℃, drying a solid-phase product and crushing to obtain a conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor;
mixing the conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor, a high molecular polymer, graphite and an organic solvent, drying to remove the organic solvent, and carbonizing and crushing a dried product.
The graphite coating material with graphite as the core and tantalum-doped lithium lanthanum zirconium oxide, amorphous carbon and conductive material coated on at least part of the surface of the graphite can be obtained by the preparation method. The preparation method can obtain a uniform coating layer, and the coating layer is beneficial to improving the lithium ion conductivity and the electronic conductivity of the graphite coating material; the rate capability, the safety performance and the cycle performance of the graphite cathode material can be effectively improved.
In some embodiments of the second aspect of the present application, the mass ratio of lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate, tantalum pentoxide, the conductive material, and water is (5-15): (20-30): (5-15), (1-3), (0.5-2): (100-500).
In some embodiments of the second aspect of the present application, the mass ratio of the conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor, the high molecular polymer, and the graphite is (1-10): 5-20): 100.
In some embodiments of the second aspect of the present application, the high molecular polymer is selected from at least one of polyethylene terephthalate, phenolic resin, polyimide, humic acid, polyethylene;
optionally, the organic solvent is selected from at least one of N-methylpyrrolidone, carbon tetrachloride, cyclohexane, dimethylformamide and tetrahydrofuran;
optionally, the mass ratio of the high molecular polymer to the organic solvent is (1-10): 100.
in some embodiments of the second aspect of the present application, the carbonization conditions for carbonizing the dried product are maintained at 700 ℃ to 1100 ℃ for 1h to 12h in a protective atmosphere.
A third aspect of the present application provides a graphite clad material obtained by the method for producing a graphite clad material according to the third aspect.
A fourth aspect of the present application provides a battery negative electrode comprising a current collector and an active material disposed on the current collector;
the active material comprises the graphite cladding material provided by the first aspect;
alternatively, the active material comprises the graphite cladding material provided in the third aspect.
The battery cathode provided by the application has the advantages of the graphite coating material, and the rate capability, the safety performance and the cycle performance of the battery can be improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is an SEM test chart of the graphite clad material prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The graphite-coated material, the preparation method thereof, and the battery negative electrode according to the embodiments of the present application will be specifically described below.
The graphite cladding material comprises an inner core and an outer shell, wherein the outer shell is wrapped outside the inner core. The inner core comprises graphite, and the outer shell comprises tantalum-doped lithium lanthanum zirconium oxide, amorphous carbon and a conductive material.
It should be noted that, in the embodiments of the present application, the relative position relationship between the tantalum-doped lithium lanthanum zirconium oxide, the amorphous carbon, and the conductive material is not limited.
For example, at least a portion of the conductive material is dispersed between at least a portion of the tantalum-doped lithium lanthanum zirconium oxide. Alternatively, the conductive material is uniformly dispersed between the tantalum-doped lithium lanthanum zirconium oxide, or at least a portion of the tantalum-doped lithium lanthanum zirconium oxide and/or at least a portion of the conductive material is in contact with the core. Or, tantalum doped lithium lanthanum zirconium oxygen, conductive material is dispersed in the amorphous carbon to form the shell.
In the application, the graphite cladding material is of a core-shell structure, the main material of the core is graphite, the outer surface of the core is coated with the shell, and the shell comprises tantalum-doped lithium lanthanum zirconium oxide, amorphous carbon and a conductive material.
In the embodiments of the present application, the graphite may be natural graphite and artificial graphite mixed in any ratio; or only natural graphite or only artificial graphite can be selected; this application is not limited thereto.
In the embodiment, the thickness of the shell is 2nm to 200 nm; for example, the shell thickness may be 2nm, 10nm, 50nm, 80nm, 100nm, 110nm, 130nm, 150nm, 190nm, or 200nm, and so forth. Too small a shell thickness can result in non-uniform coating, and if too thick, can affect the lithium ion transport rate.
The shell comprises tantalum-doped lithium lanthanum zirconium oxide, amorphous carbon and a conductive material.
The molecular formula of the tantalum-doped lithium lanthanum zirconium oxide is Ta-LiLaZrO. In some embodiments, the tantalum-doped lithium lanthanum zirconium oxide comprises 1% to 10% of the total mass of the housing; for example, tantalum-doped lithium lanthanum zirconium oxide comprises 1%, 2%, 3%, 4%, 4.5%, 5.5%, 6%, 7%, 8%, or 10% of the total mass of the housing, and so forth. The doped lithium lanthanum zirconium oxygen accounts for 1-10% of the total mass of the shell, if the proportion is too small, the effect of improving the ionic conductivity is not achieved, and if the proportion is too high, the conductivity of the shell is affected.
In some embodiments, the mass ratio of the tantalum-doped lithium lanthanum zirconium oxide to the graphite is (0.5-5): 100. for example, the mass ratio of tantalum-doped lithium lanthanum zirconium oxygen to graphite is 0.5:100, 1:100, 1.6:100, 2:100, 2.4:100, 3:100, 3.5:100, 4:100, 4.5:100, or 5:100, and so forth.
In some embodiments, the mass ratio of the tantalum-doped lithium lanthanum zirconium oxide to the conductive material is (1-10): (0.2-2). For example, the mass ratio of the conductive material doped with lithium lanthanum zirconium oxide may be 1:0.2, 2:1, 9:2, etc.
The tantalum-doped lithium lanthanum zirconium oxide has higher ionic conductivity and wider electrochemical window, and the tantalum-doped lithium lanthanum zirconium oxide has the problems of electron conductivity deviation and the like.
As an example, the conductive material may be selected from carbon nanotubes, carbon nanofibers, conductive carbon black, fullerenes, etc., which primarily function to increase electronic conductivity.
In the application, the tantalum-doped lithium lanthanum zirconium oxygen and the conductive material are doped in the surface coating layer of the graphite, so that the transmission rate and the diffusion coefficient of lithium ions can be effectively improved, and the electronic conductivity of the graphite composite material can be effectively improved by the conductive material; the amorphous carbon can improve the uniformity of the graphite surface so as to improve the first effect; the tantalum-doped lithium lanthanum zirconium oxide, the amorphous carbon and the conductive material in the shell cooperatively show good lithium ion conductivity and electronic conductivity, so that the ion transmission rate and the conductivity of the graphite coating material are favorably improved, and the multiplying power performance, the safety performance and the cycle performance of the graphite cathode material can be effectively improved.
The application also provides a preparation method of the graphite coating material, which comprises the following steps: mixing lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate, tantalum pentoxide, an oxidation conductive material and water, carrying out hydrothermal reaction for 1-12 h at 100-200 ℃, drying a solid-phase product and crushing to obtain a conductive material/tantalum-doped lithium lanthanum zirconium oxygen precursor. Mixing the conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor, a high molecular polymer, graphite and an organic solvent, drying to remove the organic solvent, and carbonizing and crushing a dried product.
In the application, lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate, tantalum pentoxide, oxidized conductive material and water are used for preparing the conductive material/tantalum-doped lithium lanthanum zirconium oxygen precursor by a hydrothermal method, so that the conductive material and the tantalum-doped lithium lanthanum zirconium oxygen can be uniformly mixed, the consistency of the material is ensured, and the ionic conductivity and the electronic conductivity of the material are exerted.
Illustratively, in some embodiments of the present application, the mass ratio of lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate, tantalum pentoxide, oxidized conductive material, and water is (5-15): (20-30): (5-15), (1-3), (0.5-2): (100-500).
As an example, the mass ratio of lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate, tantalum pentoxide, oxidized conductive material, and water may be 5: 20: 5: 1: 0.5: 100. 10: 25: 8: 2: 1: 240 or 15: 30: 15: 3: 2: 500, and so on.
In the embodiment of the present application, the high molecular polymer is selected from at least one of polyethylene terephthalate, phenol resin, polyimide, humic acid, and polyethylene; for example, in the present application, the high molecular polymer is a phenol resin. It is understood that in other embodiments of the present application, other polymers that can be carbonized to form amorphous carbon can be used as the high molecular weight polymer.
In some embodiments of the present application, the mass ratio of the conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor to the high molecular polymer to the graphite is (1-10): 5-20): 100. For example, the mass ratio of the conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor, the high molecular polymer and the graphite may be 1: 5:100, 2: 9:100, 6:13:100 or 10:20:100, etc.
In an embodiment of the present application, the organic solvent is selected from at least one of N-methylpyrrolidone, carbon tetrachloride, cyclohexane, dimethylformamide and tetrahydrofuran.
The main function of the organic solvent is to uniformly disperse the conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor, the high molecular polymer and the graphite, and the organic solvent does not react with the high molecular polymer. The organic solvent is volatile during the drying process, e.g., at 80-100 ℃.
In some embodiments of the present application, the mass ratio of the high molecular polymer to the organic solvent is (1-10): 100. for example, the mass ratio of the high molecular polymer to the organic solvent may be 1: 100. 3: 100. 5: 100. 7: 100. 8: 100. 9:100 or 10: 100, etc.
It is understood that in other embodiments of the present application, the mass ratio of lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate, tantalum pentoxide, oxidized conductive material, and water may not be within the above range regardless of the yield or yield. Accordingly, in some embodiments, the mass ratio of the conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor, the high molecular polymer, and the graphite may not be within the above range. The mass ratio of the high-molecular polymer to the organic solvent may be out of the above range.
In the embodiment of the present application, a conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor, a high molecular polymer, graphite, and an organic solvent are mixed and dried, and the dried product is carbonized and pulverized.
In an embodiment of the present application, the drying method is spray drying, and in another embodiment of the present application, the drying method may be another drying method.
In the examples of the present application, the carbonization conditions were maintained at 700 ℃ to 1100 ℃ for 1 hour to 12 hours in a protective atmosphere. For example, the protective atmosphere may be nitrogen, argon, helium, and the like.
For example, the temperature of carbonization may be 700 ℃, 750 ℃, 800 ℃, 860 ℃, 910 ℃, 1000 ℃, 1060 ℃, 1100 ℃, or the like.
The carbonization time can be 1h, 2h, 3h, 4h, 6h, 8h, 9h, 11h, 12h, or the like.
According to the preparation method provided by the embodiment of the application, the graphite coating material with graphite as the inner core and tantalum-doped lithium lanthanum zirconium oxide, amorphous carbon and conductive material coated on at least part of the surface of the graphite can be obtained. The preparation method can obtain a uniform coating layer, and the coating layer is beneficial to improving the lithium ion conductivity and the electronic conductivity of the graphite coating material; the rate capability, the safety performance and the cycle performance of the graphite cathode material can be effectively improved.
The application also provides a graphite coating material, and the graphite coating material is prepared by the preparation method of the graphite coating material.
The graphite coating material shell is provided with a uniform conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor, and the tantalum-doped lithium lanthanum zirconium oxide, graphite, amorphous carbon and the conductive material are mutually cooperated, so that the lithium ion conductivity and the electronic conductivity of the graphite coating material can be improved, and the rate capability, the safety performance and the cycle performance can be improved when the graphite coating material shell is used for preparing a battery.
The present application further provides a battery negative electrode comprising a current collector and an active material disposed on the current collector. The active material may be any of the graphite clad materials described above.
Obviously, the battery cathode provided by the application has the advantages of the graphite coating material, and the rate capability, the safety performance and the cycle performance of the battery can be improved.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
The embodiment provides a graphite coating material, which is mainly prepared by the following method:
1) dissolving 10g of lithium nitrate, 25g of lanthanum nitrate hexahydrate, 10g of zirconyl nitrate and 2g of tantalum pentoxide in 200ml of deionized water, then adding 100ml of oxidized conductive material conductive liquid with the concentration of 1 wt%, carrying out hydrothermal reaction for 6h at 150 ℃, filtering, vacuum drying at 80 ℃, and grinding to obtain the conductive material/tantalum-doped lithium lanthanum zirconium oxygen precursor.
2) Uniformly stirring 5g of conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor, 200ml of phenolic resin N-methylpyrrolidine solution with the concentration of 5 wt%, 100g of artificial graphite and 200ml of N-methylpyrrolidone, then carrying out spray drying, carbonizing at 800 ℃ for 6h after crushing, and crushing and grading to obtain the tantalum-doped lithium lanthanum zirconium oxide-coated graphite coating material.
SEM test was performed on the graphite clad material prepared in example 1, and the test results are shown in fig. 1. As can be seen from the figure, the graphite coating material is in an irregular particle shape, and a coating layer is arranged in the shell, and the particle size is between (10-20) mu m.
Example 2
The embodiment provides a graphite coating material, which is mainly prepared by the following method:
1) dissolving 5g of lithium nitrate, 20g of lanthanum nitrate hexahydrate, 5g of zirconyl nitrate and 1g of tantalum pentoxide in 100ml of deionized water, adding 100ml of oxidized conductive material conductive liquid with the concentration of 0.5 wt%, carrying out hydrothermal reaction at 100 ℃ for 12h, filtering, drying in vacuum at 80 ℃, and grinding to obtain the conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor.
2) Uniformly mixing 1g of conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor, 500ml of 1 wt% of phenolic resin cyclohexane solution, 100g of artificial graphite and 500ml of cyclohexane, spray-drying, carbonizing at 700 ℃ for 12h, and crushing and grading to obtain the tantalum-doped lithium lanthanum zirconium oxide-coated graphite coating material.
Example 3
The embodiment provides a graphite coating material, which is mainly prepared by the following method:
1) dissolving 15g of lithium nitrate, 30g of lanthanum nitrate hexahydrate, 15g of zirconyl nitrate and 3g of tantalum pentoxide in 500ml of deionized water, adding 100ml of 2 wt% conductive solution of an oxidized conductive material, carrying out hydrothermal reaction at 200 ℃ for 1h, filtering, drying in vacuum at 80 ℃, and grinding to obtain the conductive material/tantalum-doped lithium lanthanum zirconium oxygen precursor.
2) Uniformly stirring a mixed solution consisting of 10g of a conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor, 200ml of a 10 wt% phenolic resin N-methyl pyrrolidone solution, 100g of artificial graphite and 500ml of N-methyl pyrrolidone, then carrying out spray drying, carbonizing at 1100 ℃ for 1h, and crushing and grading to obtain the tantalum-doped lithium lanthanum zirconium oxide-coated graphite coating material.
Comparative example 1
The comparative example provides a graphite coating material, which is mainly prepared by the following method:
stirring 10g of phenolic resin and 100g of artificial graphite uniformly by a ball mill, carrying out hot melting at the temperature of 200 ℃, coating the phenolic resin on the surface of the graphite, transferring the graphite to a tubular furnace, carbonizing the graphite at the temperature of 800 ℃ for 6 hours, and then crushing and grading to obtain the hard carbon coated graphite coating material.
Test examples
The graphite coating materials in examples 1 to 3 and comparative example 1 were subjected to a powder conductivity test by the following method: pressing the powder into a blocky structure on a powder compaction density instrument under the pressure of 2T, and then testing the powder conductivity by adopting a four-probe tester. The test results are shown in table 1.
TABLE 1 physicochemical Properties of graphite coating materials of examples 1 to 3 and comparative example 1
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 |
| Powder conductivity (S/cm) | 6.23 | 6.18 | 6.11 | 1.85 |
| Tap density (g/cm)3) | 1.24 | 1.21 | 1.18 | 1.12 |
| Specific surface area (m)2/g) | 1.72 | 1.65 | 1.62 | 1.41 |
As can be seen from table 1, the graphite clad materials of examples 1-3 have significantly higher electrical conductivity than the graphite clad material of comparative example 1, because: the surfaces of the materials of examples 1-3 are coated with conductive materials with high conductivity, so that the transmission rate of electrons is improved; meanwhile, the outermost tantalum-doped lithium lanthanum zirconium oxide and amorphous carbon layer is also beneficial to improving the electronic conductivity of the material; in addition, the tantalum-doped lithium lanthanum zirconium oxide coated on the surface of the material has the characteristics of high density, high density and the like, so that the tap density and the specific surface area of the material are improved.
Test example 2
The graphite cladding materials provided by examples 1-3 and comparative example 1 were respectively assembled into button cells A1, A2, A3 and B1.
The assembling method comprises the following steps: mixing the negative electrode material, the binder, the conductive agent and the solvent, stirring and pulping, coating the mixture on copper foil, and drying and rolling the copper foil to obtain the negative electrode plate. The binder used was LA132 binder, the conductive agent was SP, the negative electrode material was the graphite coating material provided in examples 1 to 3 and comparative example 1, respectively, and the solvent was redistilled water.
Ratio of each componentExamples are: and (3) anode material: SP: LA 132: 95g of secondary distilled water: 1 g: 4 g: 220 mL; the electrolyte is LiPF6/EC+DEC(LiPF6The concentration of the lithium ion battery is 1.2mol/L, the volume ratio of EC to DEC is 1:1), the metal lithium sheet is used as a counter electrode, and the diaphragm is made of a Polyethylene (PE), polypropylene (PP) and polyethylene propylene (PEP) composite film. The button cell is assembled in a glove box filled with argon, and the electrochemical performance test is carried out on a Wuhan blue CT2001A type battery tester, wherein the charging and discharging voltage range is 0.005V-2.0V, and the charging and discharging multiplying power is 0.1C. The test results are shown in table 2.
Table 2 comparison of the performance of lithium ion batteries of examples 1-3 with the graphite coating material of comparative example 1
As can be seen from table 2, the first discharge capacity and the first charge-discharge efficiency of the lithium ion batteries prepared by using the graphite coating materials of examples 1 to 3 are significantly higher than those of comparative example 1, because: the surface of the graphite is coated with tantalum-doped lithium lanthanum zirconium oxide, the insertion and extraction rate of lithium ions is improved by utilizing the high lithium ion conductivity, the formation quality of an SEI film is improved, the irreversible capacity loss of the material is reduced, and the first efficiency is improved.
Test example 3
The graphite clad materials provided in examples 1 to 3 and comparative example 1 were used as negative electrode materials, respectively, to prepare negative electrode sheets. With ternary materials (LiNi)1/3Co1/3Mn1/3O2) As the positive electrode, LiPF6Solution (solvent is a mixture of EC and DEC with a volume ratio of 1:1, LiPF6Concentration of 1.3mol/L) as electrolyte and celegard2400 as diaphragm, and 5Ah soft package batteries C1, C2, C3 and D1 were prepared. Wherein C1, C2 and C3 correspond to the graphite clad materials provided in examples 1, 2 and 3, respectively, and D1 corresponds to the graphite clad material provided in comparative example 1.
The pouch cells C1, C2, C3 and D1 were tested for cycling performance, rate capability.
Cycle performance test conditions: the charging and discharging current is 1C/1C, the voltage range is 2.8-4.2V, and the cycle times are 500 times.
Multiplying power performance test conditions: charging rate: 1C/3C/5C, discharge multiplying power of 1C; voltage range: 2.8-4.2V.
The test results are shown in tables 3 and 4.
TABLE 3 cycle performance of lithium ion batteries
As can be seen from table 3, the cycle performance of the pouch batteries C1, C2 and C3 is better than that of D1, because, in the aspect of 1C/1C rate cycle performance, the pouch batteries C1, C2 and C3 improve the transmission rate of lithium ions and the electron conduction rate of the conductive material thereof by means of the tantalum-doped lithium lanthanum zirconium oxygen on the graphite surface, and further improve the cycle performance thereof by utilizing the characteristic of stable structure of the tantalum-doped lithium lanthanum zirconium oxygen.
Table 4 multiplying power charging performance comparison table
As can be seen from table 4, the constant current ratios of the soft package batteries C1, C2, and C3 are better than D1, because the tantalum-doped lithium lanthanum zirconium oxide coated on the surfaces of the materials in examples 1 to 3 effectively increases the transmission rate of lithium ions, thereby increasing the insertion and extraction rate of lithium ions during the rate charging process of the materials and increasing the rate charging performance of the batteries.
Test example 4
Needle short circuit test: the graphite coating materials in examples 1-3 and comparative example 1 were used to prepare lithium ion batteries respectively, and the safety performance was tested, with the test method referring to UL2054 safety standards, and the results are shown in table 5 below.
TABLE 5 safety Performance test results
| Item | Coefficient of safety | Temperature (. degree.C.) |
| Example 1 | 9/10 | 135 |
| Example 2 | 8/10 | 139 |
| Example 3 | 8/10 | 145 |
| Comparative example 1 | 4/10 | 176 |
As can be seen from table 5, the lithium ion batteries prepared using the graphite coating materials of examples 1-3 have a high safety factor and a low temperature rise relative to comparative example 1. The reason is that: the graphite coating materials of examples 1 to 3 have high temperature resistance, reduce the occurrence probability of thermal runaway during the short circuit of the battery, and improve the safety performance thereof.
In summary, the core provided by the embodiment of the present application includes graphite, and the graphite cladding material of which the shell includes tantalum-doped lithium lanthanum zirconium oxide, amorphous carbon and a conductive material has a better safety performance, an improved rate charging performance, and a better first efficiency.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A graphite cladding material, comprising:
an inner core comprising graphite; and
and the shell is coated outside the inner core and comprises tantalum-doped lithium lanthanum zirconium oxide, amorphous carbon and a conductive material.
2. The graphite cladding material of claim 1, wherein the tantalum-doped lithium lanthanum zirconium oxide comprises 1% to 10% of the total mass of the outer shell;
optionally, the tantalum-doped lithium lanthanum zirconium oxide accounts for 4% -8% of the total mass of the shell;
optionally, the thickness of the shell is 2nm to 200 nm.
3. The graphite cladding material of claim 1 or 2, wherein the mass ratio of the tantalum-doped lithium lanthanum zirconium oxide to the graphite is (0.5-5): 100, respectively;
optionally, the mass ratio of the tantalum-doped lithium lanthanum zirconium oxide to the graphite is (1-3): 100, respectively;
optionally, the mass ratio of the tantalum-doped lithium lanthanum zirconium oxide to the conductive material is (1-10): (0.2-2).
4. A preparation method of a graphite coating material is characterized by comprising the following steps:
mixing lithium nitrate, lanthanum nitrate hexahydrate, zirconyl nitrate, tantalum pentoxide, an oxidation conductive material and water, carrying out hydrothermal reaction for 1-12 h at 100-200 ℃, drying a solid-phase product and crushing to obtain a conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor;
mixing the conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor, a high molecular polymer, graphite and an organic solvent, drying to remove the organic solvent, and carbonizing and crushing a dried product.
5. The preparation method of the graphite cladding material according to claim 4, wherein the mass ratio of the lithium nitrate, the lanthanum nitrate hexahydrate, the zirconyl nitrate, the tantalum pentoxide, the conductive material and the water is (5-15): (20-30): (5-15), (1-3), (0.5-2): (100-500).
6. The method for preparing the graphite cladding material according to claim 4, wherein the mass ratio of the conductive material/tantalum-doped lithium lanthanum zirconium oxide precursor to the high molecular polymer to the graphite is (1-10): 5-20): 100.
7. The method for preparing a graphite clad material according to any one of claims 4 to 6, wherein the high molecular polymer is at least one selected from the group consisting of polyethylene terephthalate, phenol resin, polyimide, humic acid, and polyethylene;
optionally, the organic solvent is selected from at least one of N-methylpyrrolidone, carbon tetrachloride, cyclohexane, dimethylformamide and tetrahydrofuran;
optionally, the mass ratio of the high molecular polymer to the organic solvent is (1-10): 100.
8. the method for producing the graphite clad material according to any one of claims 4 to 6, wherein the carbonization conditions for carbonizing the dried product are maintained at 700 to 1100 ℃ for 1 to 12 hours in a protective atmosphere.
9. A graphite clad material, characterized in that it is produced by the method for producing a graphite clad material according to any one of claims 4 to 8.
10. A battery negative electrode, comprising a current collector and an active material disposed on the current collector;
the active material comprises the graphite coating material of any one of claims 1-3;
alternatively, the active material comprises the graphite cladding material of claim 9.
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| CN115000389A (en) * | 2022-07-15 | 2022-09-02 | 湖北亿纬动力有限公司 | Negative electrode material and preparation method and application thereof |
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