[go: up one dir, main page]

CN113889594A - A kind of preparation method of boron-doped lanthanum zirconate lithium-coated graphite composite material - Google Patents

A kind of preparation method of boron-doped lanthanum zirconate lithium-coated graphite composite material Download PDF

Info

Publication number
CN113889594A
CN113889594A CN202010633943.3A CN202010633943A CN113889594A CN 113889594 A CN113889594 A CN 113889594A CN 202010633943 A CN202010633943 A CN 202010633943A CN 113889594 A CN113889594 A CN 113889594A
Authority
CN
China
Prior art keywords
boron
lithium
doped
inorganic
precursor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010633943.3A
Other languages
Chinese (zh)
Inventor
徐军红
陈和平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LUOYANG YUEXING NEW ENERGY TECHNOLOGY CO LTD
Original Assignee
LUOYANG YUEXING NEW ENERGY TECHNOLOGY CO LTD
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LUOYANG YUEXING NEW ENERGY TECHNOLOGY CO LTD filed Critical LUOYANG YUEXING NEW ENERGY TECHNOLOGY CO LTD
Priority to CN202010633943.3A priority Critical patent/CN113889594A/en
Publication of CN113889594A publication Critical patent/CN113889594A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本发明属于二次电池负极材料领域，具体涉及一种硼掺杂锆酸镧锂包覆石墨复合材料的制备方法。该方法包括以下步骤：1)无机锂盐、无机镧盐、无机锆盐、硼酸盐、乙二醇、氧化石墨烯、柠檬酸和溶剂混合，制备前驱体液，将前驱体液进行水热反应，干燥，得到石墨烯/硼掺杂锆酸镧锂前驱体；2)将石墨烯/硼掺杂锆酸镧锂前驱体、无定形碳前驱体、石墨、溶剂组成的混合液进行喷雾干燥，然后将喷雾干燥产物进行碳化。该方法所得硼掺杂锆酸镧锂包覆石墨复合材料，外壳中的硼掺杂锆酸锂镧、无定形碳和石墨烯协同表现出良好的锂离子导电率和电子导电性，有利于提升材料的离子传输速率和导电性，可有效提高石墨负极材料的倍率性能、散热性能和循环性能。

Figure 202010633943

The invention belongs to the field of negative electrode materials for secondary batteries, and particularly relates to a preparation method of a boron-doped lanthanum zirconate lithium-coated graphite composite material. The method includes the following steps: 1) mixing inorganic lithium salt, inorganic lanthanum salt, inorganic zirconium salt, borate, ethylene glycol, graphene oxide, citric acid and a solvent to prepare a precursor liquid, and performing a hydrothermal reaction on the precursor liquid, drying to obtain a graphene/boron-doped lithium lanthanum zirconate precursor; 2) spray-drying a mixed solution consisting of a graphene/boron-doped lithium lanthanum zirconate precursor, an amorphous carbon precursor, graphite and a solvent, and then The spray dried product is carbonized. The boron-doped lanthanum zirconate lithium-coated graphite composite material obtained by the method, the boron-doped lithium lanthanum zirconate, amorphous carbon and graphene in the shell synergistically exhibit good lithium ion conductivity and electronic conductivity, which is beneficial to improve The ion transport rate and conductivity of the material can effectively improve the rate performance, heat dissipation performance and cycle performance of the graphite anode material.

Figure 202010633943

Description

Preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material
Technical Field
The invention belongs to the field of secondary battery cathode materials, and particularly relates to a preparation method of a boron-doped lithium lanthanum zirconate-coated graphite composite material.
Background
At present, artificial graphite is mainly used in the commercialized lithium ion battery negative electrode material, the rate performance of the artificial graphite is poor, and at present, the rate of lithium ion insertion/removal of the material is improved by coating soft carbon or hard carbon on the surface of the artificial graphite.
The application publication No. CN110071274A of the invention of China discloses a processing technology for improving the performance of an artificial graphite cathode material by a coating treatment method, which is to coat the artificial graphite by high-temperature asphalt and then coat a layer of amorphous carbon on the surface of the artificial graphite by carbonization treatment, thereby having certain improvement effect on the electrochemical performance of the artificial graphite.
Because the coating is at the charge-discharge in-process, lithium ion can only pass in and out the graphite layer structure from the edge of graphite layer, be on a parallel with the direction of graphite layer promptly, can't pass in and out from the direction of perpendicular graphite layer, so lithium ion business turn over graphite layer's diffusion coefficient is little, directly leads to lithium ion battery's multiplying power performance relatively poor. Meanwhile, during charging and discharging under high magnification, when lithium ions have no time to diffuse into the graphite layers, the lithium ions are concentrated on the surface of the negative electrode and reduced into metal lithium dendrites with extremely high activity, so that safety performance deviation is caused.
Disclosure of Invention
The invention aims to provide a preparation method of a boron-doped lanthanum lithium zirconate-coated graphite composite material, so as to improve the cycle performance and rate capability of a graphite cathode material.
In order to achieve the purpose, the technical scheme of the preparation method of the boron-doped lanthanum lithium zirconate-coated graphite composite material is as follows:
a preparation method of a boron-doped lanthanum lithium zirconate-coated graphite composite material comprises the following steps:
1) mixing inorganic lithium salt, inorganic lanthanum salt, inorganic zirconium salt, borate, glycol, graphene oxide, citric acid and a solvent to prepare a precursor liquid, carrying out hydrothermal reaction on the precursor liquid, and drying to obtain a graphene/boron-doped lanthanum lithium zirconate precursor;
2) and (2) carrying out spray drying on a mixed solution consisting of a graphene/boron-doped lanthanum lithium zirconate precursor, an amorphous carbon precursor, graphite and a solvent, and then carbonizing a spray-dried product.
The boron-doped lanthanum lithium zirconate coated graphite composite material obtained by the method is of a core-shell structure, the core is graphite, the shell mainly comprises boron-doped lanthanum lithium zirconate, amorphous carbon and graphene, and the boron-doped lanthanum lithium zirconate accounts for 10-30% of the total mass of the boron-doped lanthanum lithium zirconate and the amorphous carbon; wherein the molecular formula of the boron-doped lanthanum lithium zirconate is Li2ZrxB1-xO3，0.5≤x≤1。
According to the preparation method of the boron-doped lanthanum lithium zirconate-coated graphite composite material, the boron-doped lanthanum lithium zirconate, the amorphous carbon and the graphene in the shell cooperatively show good lithium ion conductivity and electronic conductivity, so that the ion transmission rate and the conductivity of the material can be improved, and the rate capability, the heat dissipation performance and the cycle performance of the graphite cathode material can be effectively improved.
In the method, the boron element and the graphene are uniformly doped in the coating layer by a hydrothermal method, and are uniformly mixed with the coating agent and then coated on the surface of the graphite, so that the preparation process is simple, the stability is good, and the product has high quality stability and consistency.
In order to further optimize the rate capability and the cycle performance of the graphite cathode material, preferably, the mass ratio of the boron-doped lanthanum lithium zirconate in the shell to the graphite core is (1-10): 100.
in order to enable the composite material to have higher tap density and improve the energy density of the battery, the particle size of the boron-doped lithium lanthanum zirconate-coated graphite composite material is preferably 10-20 mu m.
The hydrothermal reaction is carried out only by ensuring that all raw materials are fully reacted, and preferably, in terms of reaction efficiency, in the step 1), the temperature of the hydrothermal reaction is 150-200 ℃, and the reaction time is 1-12 hours.
In order to control the formation of precursor particles with uniform particle size, preferably, in step 1), the inorganic lithium salt is one or more than two of lithium nitrate, lithium carbonate and lithium hydroxide; one or more of inorganic lanthanum salt lanthanum nitrate and lanthanum carbonate; the inorganic zirconium salt is one or more of zirconium nitrate, zirconium phosphate, zirconium carbonate and zirconium hydroxide; the borate is one or two of sodium tetraphenylborate and tetraphenylboronic acid;
the mass ratio of the inorganic lithium salt to the inorganic lanthanum salt to the inorganic zirconium salt to the borate to the ethylene glycol to the graphene oxide is 5: (10-15), (5-10), (1-3): (5-8): (0.5 to 3); the molar ratio of the ethylene glycol to the citric acid is (1-3) to 1. The citric acid has a reduction effect, the glycol can play a role in controlling nucleation and crystallization, and the glycol and the citric acid can be used together to control the generation of the graphene/boron-doped lanthanum lithium zirconate precursor with regular and consistent appearance, so that good conditions are created for the electrical performance of the electrode material.
In order to facilitate the uniform mixing of citric acid and graphene oxide, preferably, in step 1), mixing an inorganic lithium salt, an inorganic lanthanum salt, an inorganic zirconium salt, a borate and a solvent, then adding a citric acid solution, ethylene glycol and a graphene oxide solution, and uniformly mixing, wherein the concentration of the citric acid solution is (1-10)%, and the concentration of the graphene oxide solution is (1-5)%.
In order to improve the coating consistency of the coating layer, preferably, in the step 2), the mass ratio of the graphene/boron-doped lanthanum lithium zirconate precursor to the amorphous carbon precursor to the graphite is (1-10): 5-20): 100.
In order to realize better wrapping and dispersion of boron-doped lanthanum lithium zirconate and graphene, preferably, in the step 2), the amorphous carbon precursor is pitch.
The carbonization reaction can promote the amorphous carbon precursor to be fully converted into the amorphous carbon, preferably, in the step 2), the carbonization is carried out for 1-12 hours at 700-1100 ℃ in a protective atmosphere.
Drawings
Fig. 1 is an SEM image of the boron-doped lanthanum lithium zirconate-coated graphite composite material according to example 1 of the present invention.
Detailed Description
The following examples are provided to further illustrate the practice of the invention.
First, a specific embodiment of the preparation method of the boron-doped lanthanum lithium zirconate-coated graphite composite material
Example 1
The preparation method of the boron-doped lanthanum lithium zirconate-coated graphite composite material comprises the following steps:
1) preparation of precursor liquid: adding 5g of lithium nitrate, 12g of lanthanum nitrate, 8g of zirconium nitrate and 2g of sodium tetraphenylborate into 100ml of deionized water, uniformly mixing, adding 760ml of a 5% citric acid solution with a mass concentration, 6.2g of ethylene glycol and 100ml of a 3% graphene oxide solution with a mass concentration (the molar ratio of the ethylene glycol to the citric acid is 2:1), and uniformly dispersing by ultrasonic to obtain a precursor solution.
2) Transferring the precursor liquid into a high-pressure reaction kettle, reacting for 6 hours at 180 ℃, then naturally cooling to room temperature, and drying to obtain a graphene/boron-doped lithium lanthanum zirconate precursor; and then uniformly mixing 5g of graphene/boron-doped lanthanum lithium zirconate precursor with 10g of pitch, dispersing the mixture in 1000ml of n-hexane organic solvent, adding 100g of artificial graphite, uniformly stirring, carrying out spray drying, heating the obtained spray-dried particles to 800 ℃ in an argon inert gas environment, keeping the temperature at the constant temperature for 6 hours, and naturally cooling to room temperature to obtain the graphene/boron-doped lanthanum lithium zirconate/amorphous carbon coated modified artificial graphite cathode material.
The boron-doped lanthanum lithium zirconate-coated graphite composite material prepared by the method has a core-shell structure, the inner core is artificial graphite, the shell mainly comprises boron-doped lanthanum lithium zirconate, amorphous carbon and graphene, and the boron-doped lanthanum lithium zirconate Li is2ZrxB1- xO3(x is more than or equal to 0.5 and less than or equal to 1), the boron-doped lanthanum lithium zirconate accounts for 20 percent of the total mass of the boron-doped lanthanum lithium zirconate and the amorphous carbon, and the mass ratio of the boron-doped lanthanum lithium zirconate in the artificial graphite core to the shell is 100: 5.
Example 2
The preparation method of the boron-doped lanthanum lithium zirconate-coated graphite composite material comprises the following steps:
1) preparation of precursor liquid: adding 5g of lithium carbonate, 10g of lanthanum carbonate, 5g of zirconium phosphate and 1g of tetraphenyl boric acid into 100ml of deionized water, uniformly mixing, then adding 192ml of a 1% citric acid solution with a mass concentration, 6.2g of ethylene glycol and 50ml of a 1% graphene oxide solution with a mass concentration (the molar ratio of the ethylene glycol to the citric acid is 1:1), and uniformly dispersing by ultrasonic to obtain a precursor solution;
2) transferring the precursor liquid into a high-pressure reaction kettle, reacting at 150 ℃ for 12h, naturally cooling to room temperature, and drying to obtain a graphene/boron-doped lanthanum lithium zirconate precursor; and then uniformly mixing 1g of graphene/boron-doped lanthanum lithium zirconate precursor with 5g of pitch, dispersing the mixture in 1000ml of tetrahydrofuran organic solvent, adding 100g of artificial graphite, uniformly stirring, carrying out spray drying, heating the spray-dried particles to 700 ℃ in an argon inert gas environment, keeping the temperature at a constant temperature for 12h, and naturally cooling to room temperature to obtain the graphene/boron-doped lanthanum lithium zirconate/carbon-coated modified artificial graphite cathode material.
The boron-doped lanthanum lithium zirconate-coated graphite composite material obtained by the method of the embodiment has a core-shell structure, the inner core is artificial graphite, the shell mainly comprises boron-doped lanthanum lithium zirconate, amorphous carbon and graphene, and the molecular formula of the boron-doped lanthanum lithium zirconate is Li2ZrxB1-xO3(x is more than or equal to 0.5 and less than or equal to 1), the boron-doped lanthanum lithium zirconate accounts for 10 percent of the total mass of the boron-doped lanthanum lithium zirconate and the amorphous carbon, and the mass ratio of the boron-doped lanthanum lithium zirconate in the artificial graphite core to the shell is 100: 1.
Example 3
The preparation method of the boron-doped lanthanum lithium zirconate-coated graphite composite material comprises the following steps:
1) preparation of precursor liquid: adding 5g of lithium hydroxide, 15g of lanthanum nitrate, 10g of zirconium carbonate and 3g of sodium tetraphenylborate into 100ml of deionized water, uniformly mixing, adding 57ml of a 10% citric acid solution, 6.2g of ethylene glycol and 40ml of a 5% graphene oxide solution (the molar ratio of the ethylene glycol to the citric acid is 3:1), and uniformly dispersing by ultrasonic to obtain a precursor solution;
2) transferring the precursor liquid into a high-pressure reaction kettle, reacting at 200 ℃ for 1h, naturally cooling to room temperature, and drying to obtain a graphene/boron-doped lanthanum lithium zirconate precursor; and then, uniformly mixing 10g of graphene/boron-doped lanthanum lithium zirconate precursor with 20g of asphalt, dispersing the mixture in 1000ml of carbon disulfide organic solvent, adding 100g of artificial graphite, uniformly stirring, carrying out spray drying, heating the spray-dried particles to 1100 ℃ in an argon inert gas environment, keeping the temperature at a constant temperature for 1h, and naturally cooling to room temperature to obtain the graphene/boron-doped lanthanum lithium zirconate/carbon-coated modified artificial graphite cathode material.
The boron-doped lanthanum lithium zirconate-coated graphite composite material obtained by the method of the embodiment has a core-shell structure, the inner core is artificial graphite, the shell mainly comprises boron-doped lanthanum lithium zirconate, amorphous carbon and graphene, and the molecular formula of the boron-doped lanthanum lithium zirconate is Li2ZrxB1-xO3(x is more than or equal to 0.5 and less than or equal to 1), the boron-doped lanthanum lithium zirconate accounts for 30 percent of the total mass of the boron-doped lanthanum lithium zirconate and the amorphous carbon, and the mass ratio of the boron-doped lanthanum lithium zirconate in the artificial graphite core to the shell is 100: 10.
Second, comparative example
Comparative example 1
Adding 20g of pitch and 40ml of graphene oxide solution with the mass concentration of 5% into 1000ml of tetrahydrofuran, uniformly stirring, adding 100g of artificial graphite, uniformly stirring, performing spray drying to obtain a precursor material, transferring the precursor material into a tubular furnace, heating to 800 ℃ under the argon atmosphere, preserving heat for 3 hours, and naturally cooling to room temperature to obtain the amorphous carbon coated artificial graphite composite material.
Third, Experimental example
Experimental example 1SEM test
The boron-doped lanthanum lithium zirconate-coated graphite composite material prepared in example 1 was subjected to SEM test, and the results are shown in fig. 1.
As can be seen from figure 1, the obtained boron-doped lanthanum lithium zirconate-coated graphite composite material is granular, the particle size is between 10 and 20 microns, and the size distribution is uniform and reasonable.
Experimental example 2 button cell test
The graphite composites of the examples and comparative examples were assembled into button cells, respectively, and labeled: the button cell assembled from the graphite composite material of example 1 was labeled a1, the button cell assembled from the graphite composite material of example 2 was labeled a2, the button cell assembled from the graphite composite material of example 3 was labeled A3, and the button cell assembled from the graphite composite material of comparative example was labeled B1.
The preparation method of the button cell comprises the following steps: and adding a binder, a conductive agent and a solvent into the graphite composite material, stirring and mixing uniformly for pulping, coating the obtained slurry on a copper foil, drying and rolling to obtain the button cell. The adhesive is LA132 adhesive, the conductive agent is conductive agent SP, and the solvent is secondary distilled water; and the weight ratio of the graphite composite material, the conductive agent SP, the LA132 adhesive and the secondary distilled water is as follows: 95:1:4:220.
The lithium metal sheet is used as a counter electrode, a Polyethylene (PE), polypropylene (PP) or polyethylene propylene (PEP) composite membrane is used as a diaphragm, and LiPF is used6The electrolyte solution of/EC + DEC (1:1) was used to simulate cell assembly in a hydrogen-filled glove box. Button cells A1, A2, A3 and B1 are respectively installed on a Wuhan blue electricity CT2001A type battery tester, charging is carried out at 0.1C multiplying power, the charging and discharging voltage range is 0.005V to 2.0V, and the measured first discharge capacity and first discharge efficiency are shown in table 1:
TABLE 1 Studies of the Properties of examples 1-3 and comparative graphite composites
Figure BDA0002567092160000051
As can be seen from Table 1, the discharge capacities of the composite anode materials prepared in examples 1 to 3 were significantly higher than those of the comparative examples; the reason is that the surface of the graphite material is coated with the boron-doped lanthanum lithium zirconate material with high lithium ion conductivity, so that the irreversible loss of the material is reduced, the ion conductivity of the material is improved, and the first efficiency of the material is improved; meanwhile, the electronic conductivity of the lanthanum lithium zirconate solid electrolyte is improved after the boron and the graphene are doped, so that the multiplying power performance of the lanthanum lithium zirconate solid electrolyte is improved.
Experimental example 3 pouch cell test
The materials prepared in examples 1 to 3 and comparative example were used as anode materials, respectively, and a ternary material (LiNi) was used1/3Co1/ 3Mn1/3O2) As the positive electrode, LiPF6(the solvent is EC + DEC, the volume ratio is 1:1, and the concentration is 1.3mol/L) is electrolyte, and celegard2400 is a diaphragm to prepare the 2Ah soft package battery.
3.1 Rate Performance test
The charging and discharging voltage range is 2.8-4.2V, and charging is carried out at 1.0C, 3.0C, 5.0C and 8.0C and discharging is carried out at 1.0C under the condition that the temperature is 25 +/-3.0 ℃; the cells were tested for constant current ratio and temperature in different charging modes and the results are shown in table 2:
TABLE 2 Rate Performance of examples 1-3 and comparative examples
Figure BDA0002567092160000061
As can be seen from table 2, the rate charging performance of the pouch cell of the example is significantly better than that of the comparative example, and the charging time is shorter, indicating that the graphite composite material of the present invention has good quick charging performance. The battery needs lithium ion migration in the charging process, the surface of the graphite composite material of the embodiment contains more lithium ions, so that convenience is provided for lithium ion insertion and extraction, the multiplying power performance of the battery is improved, meanwhile, the electronic conductivity of the lanthanum lithium zirconate is improved after boron doping, and the temperature rise of the lanthanum lithium zirconate is reduced.
3.2 cycle Performance test
The following experiments were carried out on the pouch batteries prepared from the negative electrode materials of examples 1 to 3 and comparative example: the capacity retention rate was measured by sequentially performing 50, 100, and 200 cycles of charge and discharge with a charge and discharge current of 2C/2C and a voltage range of 2.8-4.2V, and the results are shown in Table 3:
TABLE 3 cyclability of the lithium ion batteries of examples 1-3 and comparative example
Figure BDA0002567092160000062
As can be seen from Table 3, the cycle performance of the lithium ion batteries prepared by using the graphite composite negative electrode materials obtained in examples 1-3 is obviously superior to that of the comparative examples at each stage. The fact that the boron-doped lanthanum lithium zirconate, the amorphous carbon and the graphene are coated on the surface of the graphite proves that the transmission rate of lithium ions can be improved, so that the cycle performance of the lithium ions is improved.

Claims (7)

1.一种硼掺杂锆酸镧锂包覆石墨复合材料的制备方法，其特征在于，包括以下步骤：1. a preparation method of boron-doped lanthanum zirconate lithium-coated graphite composite material, is characterized in that, comprises the following steps: 1)无机锂盐、无机镧盐、无机锆盐、硼酸盐、乙二醇、氧化石墨烯、柠檬酸和溶剂混合，制备前驱体液，将前驱体液进行水热反应，干燥，得到石墨烯/硼掺杂锆酸镧锂前驱体；1) Inorganic lithium salt, inorganic lanthanum salt, inorganic zirconium salt, borate, ethylene glycol, graphene oxide, citric acid and solvent are mixed to prepare a precursor liquid, and the precursor liquid is subjected to a hydrothermal reaction and dried to obtain graphene/ Boron-doped lanthanum zirconate lithium precursor; 2)将石墨烯/硼掺杂锆酸镧锂前驱体、无定形碳前驱体、石墨、溶剂组成的混合液进行喷雾干燥，然后将喷雾干燥产物进行碳化。2) spray-drying a mixed solution consisting of a graphene/boron-doped lithium lanthanum zirconate precursor, an amorphous carbon precursor, graphite, and a solvent, and then carbonizing the spray-dried product. 2.如权利要求1所述的硼掺杂锆酸镧锂包覆石墨复合材料的制备方法，其特征在于，步骤1)中，水热反应的温度为150～200℃，反应时间为1～12h。2 . The preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material according to claim 1 , wherein in step 1), the temperature of the hydrothermal reaction is 150-200° C., and the reaction time is 1- 12h. 3.如权利要求1所述的硼掺杂锆酸镧锂包覆石墨复合材料的制备方法，其特征在于，步骤1)中，无机锂盐为硝酸锂、碳酸锂、氢氧化锂中的一种或两种以上；无机镧盐硝酸镧，碳酸镧中的一种或两种以上；无机锆盐为硝酸锆、磷酸锆、碳酸锆、氢氧化锆中的一种或两种以上；硼酸盐为四苯硼酸钠、四苯硼酸中的一种或两种；3. The preparation method of boron-doped lanthanum zirconate lithium-coated graphite composite material as claimed in claim 1, wherein in step 1), the inorganic lithium salt is one of lithium nitrate, lithium carbonate and lithium hydroxide one or more of inorganic lanthanum salts lanthanum nitrate and lanthanum carbonate; inorganic zirconium salts are one or more of zirconium nitrate, zirconium phosphate, zirconium carbonate and zirconium hydroxide; boric acid The salt is one or both of sodium tetraphenylborate and tetraphenylboronic acid; 无机锂盐、无机镧盐、无机锆盐、硼酸盐、乙二醇、氧化石墨烯的质量比为5：(10～15):(5～10):(1～3)：(5～8)：(0.5～3)；乙二醇、柠檬酸的摩尔比为(1～3):1。The mass ratio of inorganic lithium salt, inorganic lanthanum salt, inorganic zirconium salt, borate, ethylene glycol and graphene oxide is 5:(10～15):(5～10):(1～3):(5～ 8): (0.5～3); the molar ratio of ethylene glycol and citric acid is (1～3):1. 4.如权利要求1-3中任一项所述的硼掺杂锆酸镧锂包覆石墨复合材料的制备方法，其特征在于，步骤1)中，先将无机锂盐、无机镧盐、无机锆盐、硼酸盐和溶剂混合，然后添加柠檬酸溶液、乙二醇、氧化石墨烯溶液混合均匀，柠檬酸溶液的浓度为(1～10)％，氧化石墨烯溶液的浓度为(1～5)％。4. The preparation method of boron-doped lanthanum zirconate lithium-coated graphite composite material according to any one of claims 1-3, characterized in that, in step 1), first inorganic lithium salt, inorganic lanthanum salt, Inorganic zirconium salt, borate and solvent are mixed, then add citric acid solution, ethylene glycol, graphene oxide solution and mix evenly, the concentration of citric acid solution is (1～10)%, and the concentration of graphene oxide solution is (1 ~5)%. 5.如权利要求1所述的硼掺杂锆酸镧锂包覆石墨复合材料的制备方法，其特征在于，步骤2)中，石墨烯/硼掺杂锆酸镧锂前驱体、无定形碳前驱体、石墨的质量比为(1～10):(5～20):100。5. The preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material according to claim 1, wherein in step 2), graphene/boron-doped lithium lanthanum zirconate precursor, amorphous carbon The mass ratio of the precursor and the graphite is (1-10):(5-20):100. 6.如权利要求1所述的硼掺杂锆酸镧锂包覆石墨复合材料的制备方法，其特征在于，步骤2)中，所述无定形碳前驱体为沥青。6 . The method for preparing a boron-doped lithium lanthanum zirconate-coated graphite composite material according to claim 1 , wherein, in step 2), the amorphous carbon precursor is pitch. 7 . 7.如权利要求1-3、5、6中任一项所述的硼掺杂锆酸镧锂包覆石墨复合材料的制备方法，其特征在于，步骤2)中，所述碳化是在保护气氛下于700～1100℃，保持1～12h。7. The preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material according to any one of claims 1-3, 5, and 6, characterized in that, in step 2), the carbonization is in the protection of Under the atmosphere at 700 ~ 1100 ℃, keep for 1 ~ 12h.
CN202010633943.3A 2020-07-02 2020-07-02 A kind of preparation method of boron-doped lanthanum zirconate lithium-coated graphite composite material Pending CN113889594A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010633943.3A CN113889594A (en) 2020-07-02 2020-07-02 A kind of preparation method of boron-doped lanthanum zirconate lithium-coated graphite composite material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010633943.3A CN113889594A (en) 2020-07-02 2020-07-02 A kind of preparation method of boron-doped lanthanum zirconate lithium-coated graphite composite material

Publications (1)

Publication Number Publication Date
CN113889594A true CN113889594A (en) 2022-01-04

Family

ID=79012728

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010633943.3A Pending CN113889594A (en) 2020-07-02 2020-07-02 A kind of preparation method of boron-doped lanthanum zirconate lithium-coated graphite composite material

Country Status (1)

Country Link
CN (1) CN113889594A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114122358A (en) * 2021-11-10 2022-03-01 云南中晟新材料有限责任公司 Quick-filling graphite composite material and preparation method thereof
CN114497507A (en) * 2022-01-29 2022-05-13 辽宁中宏能源新材料股份有限公司 Quick-filling graphite composite material and preparation method thereof
CN115241526A (en) * 2022-08-03 2022-10-25 格龙新材料科技(常州)有限公司 Artificial graphite composite material and preparation method thereof
CN115275168A (en) * 2022-09-01 2022-11-01 新疆天宏基科技有限公司 A high-rate lithium-ion battery negative electrode material and preparation method thereof
CN115663157A (en) * 2022-11-16 2023-01-31 晖阳(贵州)新能源材料有限公司 Hard carbon composite material for lithium ion battery and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107579239A (en) * 2017-09-13 2018-01-12 山东大学 A kind of graphene/solid electrolyte composite coating silicon composite negative electrode and preparation method thereof
CN107946576A (en) * 2017-11-21 2018-04-20 中航锂电（洛阳）有限公司 A kind of high magnification graphite cathode material and preparation method thereof, lithium ion battery
CN108206276A (en) * 2016-12-19 2018-06-26 天津国安盟固利新材料科技股份有限公司 A kind of lithium ion anode material of compound coating and preparation method thereof
CN108987687A (en) * 2018-06-22 2018-12-11 中南大学 A kind of low-temperature lithium ion battery graphite cathode material and preparation method thereof
CN110880594A (en) * 2019-11-13 2020-03-13 星恒电源股份有限公司 Double-coated composite solid lithium manganate material and preparation method thereof
CN111048757A (en) * 2019-12-12 2020-04-21 中南大学 B, N co-doped graphene-coated silicon nano-anode material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108206276A (en) * 2016-12-19 2018-06-26 天津国安盟固利新材料科技股份有限公司 A kind of lithium ion anode material of compound coating and preparation method thereof
CN107579239A (en) * 2017-09-13 2018-01-12 山东大学 A kind of graphene/solid electrolyte composite coating silicon composite negative electrode and preparation method thereof
CN107946576A (en) * 2017-11-21 2018-04-20 中航锂电（洛阳）有限公司 A kind of high magnification graphite cathode material and preparation method thereof, lithium ion battery
CN108987687A (en) * 2018-06-22 2018-12-11 中南大学 A kind of low-temperature lithium ion battery graphite cathode material and preparation method thereof
CN110880594A (en) * 2019-11-13 2020-03-13 星恒电源股份有限公司 Double-coated composite solid lithium manganate material and preparation method thereof
CN111048757A (en) * 2019-12-12 2020-04-21 中南大学 B, N co-doped graphene-coated silicon nano-anode material and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114122358A (en) * 2021-11-10 2022-03-01 云南中晟新材料有限责任公司 Quick-filling graphite composite material and preparation method thereof
CN114497507A (en) * 2022-01-29 2022-05-13 辽宁中宏能源新材料股份有限公司 Quick-filling graphite composite material and preparation method thereof
CN115241526A (en) * 2022-08-03 2022-10-25 格龙新材料科技(常州)有限公司 Artificial graphite composite material and preparation method thereof
CN115275168A (en) * 2022-09-01 2022-11-01 新疆天宏基科技有限公司 A high-rate lithium-ion battery negative electrode material and preparation method thereof
CN115663157A (en) * 2022-11-16 2023-01-31 晖阳(贵州)新能源材料有限公司 Hard carbon composite material for lithium ion battery and preparation method thereof
CN115663157B (en) * 2022-11-16 2023-09-01 晖阳(贵州)新能源材料有限公司 A kind of hard carbon composite material for lithium ion battery and preparation method thereof

Similar Documents

Publication Publication Date Title
WO2022166059A1 (en) Boron-doped resin-coated artificial graphite material
CN108878956B (en) Lithium-ion secondary battery
CN102790217B (en) Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof
CN112886015B (en) A three-dimensional carbon-silicon composite material
CN113889594A (en) A kind of preparation method of boron-doped lanthanum zirconate lithium-coated graphite composite material
JP2022553657A (en) Cobalt-Free Cathode Materials and Preparation Methods Thereof, and Lithium Ion Battery Cathodes and Lithium Batteries
WO2022121281A1 (en) Self-filling coated silicon-based composite material and preparation method therefor and application thereof
WO2021217617A1 (en) Negative electrode active material, manufacturing method therefor, secondary battery, and device comprising secondary battery
CN113555539A (en) A high-energy-density fast-charging graphite composite negative electrode material and preparation method thereof, and lithium ion battery
CN105355908A (en) Composite negative electrode material for lithium ion battery, preparing method thereof, negative electrode using material and lithium ion battery
CN115566170B (en) Preparation method of high-energy-density quick-charging lithium ion battery anode material
CN112133896A (en) High-capacity graphite-silicon oxide composite material and preparation method and application thereof
CN117766742B (en) Porous silicon-carbon composite material, preparation method thereof and application in secondary battery
CN1315207C (en) Composite negative pole material of Li-ion battery and its preparing process
EP3955348B1 (en) Negative electrode active material and method for preparation thereof, secondary battery, and apparatus including secondary battery
CN113196524B (en) Negative electrode material, negative electrode sheet, electrochemical device, and electronic device
WO2023197807A1 (en) Positive electrode material and preparation method therefor, composite positive electrode material, positive electrode sheet, and secondary battery
JP7579874B2 (en) Method for producing modified graphite, secondary battery, battery module, battery pack, and power consumption device
CN116207264A (en) A positive electrode lithium supplement slurry, preparation method and application, lithium ion battery
CN115172680A (en) High-capacity high-rate lithium ion battery and preparation method thereof
CN117063306A (en) Secondary battery and electricity utilization device
CN116914293B (en) Battery cell
CN114975955B (en) Silicon-based material and battery
CN108122684A (en) Li4Ti5O12/ graphene composite material and preparation method and its cathode and application
CN119381398A (en) Positive electrode sheet, preparation method, lithium ion battery and power-consuming device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20220104