CN110752364A - Composite material, preparation method and application thereof, electrode and lithium ion battery - Google Patents
Composite material, preparation method and application thereof, electrode and lithium ion battery Download PDFInfo
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- CN110752364A CN110752364A CN201911011296.6A CN201911011296A CN110752364A CN 110752364 A CN110752364 A CN 110752364A CN 201911011296 A CN201911011296 A CN 201911011296A CN 110752364 A CN110752364 A CN 110752364A
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- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- 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
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
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- 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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- 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
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- H—ELECTRICITY
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- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a composite material, and a preparation method and application thereof, an electrode and a lithium ion battery, and belongs to the technical field of battery materials. The preparation method of the composite material comprises the following steps: mixing MXene with a transition metal salt solution, and then sequentially filtering and drying to obtain MXene particles loaded with the transition metal salt; carrying out high-temperature chemical vapor deposition on MXene particles loaded with transition metal salts and a carbon source to obtain a first product; carrying out acid passivation treatment on the first product; carrying out high-temperature chemical vapor deposition on the first product subjected to the acid passivation treatment and a silicon source to obtain a second product; and carrying out high-temperature chemical vapor deposition on the second product and a carbon source to obtain the composite material. The preparation method provided by the embodiment of the invention can effectively combine MXene, a carbon source and a silicon source, thereby greatly improving the capacity, rate capability and cycling stability of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a composite material, a preparation method and application thereof, an electrode and a lithium ion battery.
Background
The lithium ion battery has a series of advantages of high specific capacity, stable working voltage, good safety, no memory effect and the like, so the lithium ion battery is widely applied to various portable electronic instruments and equipment such as notebook computers, mobile phones, instruments and meters and the like. With the rapid development of various electronic devices and electric vehicles, people have higher and higher requirements on the energy and cycle life of lithium ion batteries. The cathode material is an important component of the battery, and together with the anode material, the cathode material determines the key performances of the lithium ion battery, such as cycle life, capacity, safety and the like, and becomes a key point of research in various countries. The current commercial graphite negative electrode material has low specific capacity which is only 372mAh/g, so that the improvement of the overall capacity of the lithium ion battery is limited, and the market demand can not be met. According to the report, the theoretical lithium storage capacity of silicon is up to 4200mAh/g, the lithium embedding platform is slightly higher than graphite, and the potential safety hazard is small; however, since silicon shows a volume change of up to 300% during charging and discharging, pulverization of silicon particles, destruction of a conductive network inside an electrode, and poor conductivity are easily caused.
In recent years, the characteristics of large specific surface area, short ion transmission path and the like of a two-dimensional material show great advantages in the field of energy storage, and MXene is a two-dimensional transition metal carbide with a graphene-like structure, has high specific surface area, good conductivity and hydrophilicity, and is expected to be used as an ideal matrix material for constructing a nano composite structure to improve the conductivity of the composite material. Although, the composite material formed by compounding MXene and nano silicon in the prior art can relieve the volume effect of the silicon material and improve the cycle performance of the material; however, the lithium ion battery prepared by the composite material has the problem of poor rate capability.
Disclosure of Invention
An object of an embodiment of the present invention is to provide a method for preparing a composite material, so as to solve the problems in the background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a method of making a composite material comprising the steps of:
(1) mixing MXene and a transition metal salt solution under a vacuum condition, and then sequentially filtering and drying to obtain MXene particles loaded with the transition metal salt;
(2) carrying out high-temperature chemical vapor deposition on MXene particles loaded with transition metal salts and a carbon source under a protective atmosphere to obtain a first product deposited with carbon nanotubes;
(3) carrying out acid passivation treatment on the first product;
(4) carrying out high-temperature chemical vapor deposition on the first product subjected to the acid passivation treatment and a silicon source under a protective atmosphere to obtain a second product deposited with nano-silicon;
(5) and carrying out high-temperature chemical vapor deposition on the second product and a carbon source under a protective atmosphere to form a carbon coating layer, thereby obtaining the composite material.
Preferably, the molecular formula of MXene is Ma+1Xa(ii) a Wherein, M atomic layers are stacked in a hexagonal close packing manner, X atoms are filled in octahedral vacancies to form an MX layer, and M is one or more of Ti, Zr, Cr, Mo, V and Ta; x is C or N.
Preferably, MXene is Ti3C2、Ti2C and Ti4C3One kind of (1).
Preferably, the transition metal salt solution is one or more of a nitrate solution, a chloride solution, a sulfate solution and an oxalate solution of the transition metal; the transition metal is one or more of iron, cobalt, nickel and chromium.
Preferably, the concentration of the transition metal salt solution is 0.1-10 mol/L.
Preferably, in the steps (2) and (5), the carbon source is one or more of acetylene, ethylene, methane, ethane, propane and n-butane.
Preferably, in the steps (2), (4) and (5), the temperature of the high-temperature chemical vapor deposition is 500-1000 ℃ independently.
Preferably, in the steps (2), (4) and (5), the protective atmosphere is nitrogen and/or argon atmosphere.
Preferably, in the step (3), the acid passivation treatment method comprises: soaking the first product in acid for 0.5-6 h, and then sequentially carrying out cleaning, dehydration and drying treatment; the acid is one or more of nitric acid, hydrochloric acid and sulfuric acid.
Preferably, in the step (4), the silicon source is one or more of monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, monomethyltrichlorosilane, dimethyltrichlorosilane, and trimethylmonochlorosilane.
Preferably, the step (5) specifically comprises the following steps:
carrying out high-temperature chemical vapor deposition on the second product and a carbon source under a protective atmosphere to obtain a third product deposited with a carbon coating layer;
mixing the third product with a carbon material to obtain the composite material; the carbon material is one or more of natural graphite, artificial graphite, mesocarbon microbeads, soft carbon and hard carbon; the particle size of the carbon material is 1-60 mu m, and the mass of the carbon material is 0-90% of the mass of the whole composite material.
Another object of the embodiments of the present invention is to provide a composite material prepared by the above preparation method; the mass ratio of the nano silicon to the MXene to the carbon nano tube in the composite material is (5-80): (1-40): 1-10).
Another object of the embodiments of the present invention is to provide a use of the above composite material as a battery material.
Another object of an embodiment of the present invention is to provide an electrode, which is partially or completely coated with the above composite material.
Preferably, the preparation method of the electrode comprises the following steps:
mixing the composite material with polyvinylidene fluoride and conductive graphite to obtain active slurry; the mass ratio of the composite material to the polyvinylidene fluoride to the conductive graphite is (90-95): (4-6): 1-4);
and coating the active slurry on a metal foil to obtain the electrode.
Another object of an embodiment of the present invention is to provide a lithium ion battery, which includes the above electrode, and the electrode is used as a negative electrode of the lithium ion battery.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
according to the preparation method of the composite material provided by the embodiment of the invention, the high-capacity nano silicon is loaded by introducing the carbon nano tube composite network structure with the elastic characteristic between MXene lamellar frameworks, so that the volume expansion of the nano silicon is met, and the structural integrity of the cathode material is favorably kept; meanwhile, the silicon nanoparticles are positioned in a three-dimensional conductive network structure constructed by multiple layers of MXene and carbon nanotubes or carbon nanofibers, and the conductivity of the silicon nanoparticles is greatly improved. Therefore, MXene, the carbon nano tube and the silicon material are effectively combined, and the capacity, rate capability and cycling stability of the lithium ion battery can be greatly improved.
Specifically, in the embodiment of the invention, MXene with good hydrophilicity is adopted as the base material, and the MXene is easy to be matched with Fe in the transition metal salt solution2+、Co2+、Ni2+And the ions can be uniformly dispersed in nano and submicron gaps between MXene sheets, so that the carbon nano tubes formed in the chemical vapor deposition process can be supported between the MXene sheets to form carbon nano bridges, the surface area and the interlayer spacing of the MXene sheets are remarkably increased, and free space can be provided for nano silicon to buffer the volume expansion of the nano silicon during energy storage. In addition, the carbon coating layer formed by the preparation method can prevent the direct contact of the electrolyte and silicon, and is beneficial to keeping the structural integrity of the cathode material, so that the capacity, the cycle performance and the service life of the battery can be improved. Meanwhile, MXene and nano silicon are connected with a conductive network formed by the carbon nano tubes, so that the conductivity of the silicon is greatly improved, and the conductive network is Li in the process of charging and discharging the battery+The transmission of (a) provides a channel which is beneficial to shortening the transmission path of electrons, thereby improving the charge and discharge rate and rate performance of the battery.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a composite material and a preparation method thereof, and particularly the preparation method of the composite material comprises the following steps:
(1) mixing MXene and a transition metal salt solution under a vacuum condition, and then sequentially filtering and drying to obtain MXene particles loaded with the transition metal salt; wherein the transition metal salt solution is ferric nitrate solution, MXene is commercial product, and its molecular formula is Ti3C2(ii) a Specifically, 10g of MXene is put into a reaction container, a vacuum pump is started to enable the vacuum degree of the reaction container to reach 0.06MPa, and then the vacuum pump is closed; then 1L of ferric nitrate solution with the molar concentration of 1mol/L is added into a reaction vessel according to the speed of 40mL/min, stirred for 30min at the rotating speed of 100r/min, and then dried for 6h at the temperature of 80 ℃ to obtain MXene particles loaded with transition metal salt.
(2) Carrying out high-temperature chemical vapor deposition on MXene particles loaded with transition metal salts and a carbon source under a protective atmosphere to obtain a first product deposited with carbon nanotubes; wherein the protective atmosphere is nitrogen atmosphere, and the carbon source is ethane; specifically, the MXene particles loaded with the transition metal salt are placed in a rotary furnace, ethane is introduced at the flow rate of 1L/min in a nitrogen atmosphere with the flow rate of 100L/min and an environment with the temperature of 800 ℃ for 1h to generate the carbon nano tube, then the nitrogen introduction is switched, and the carbon nano tube is naturally cooled to the room temperature to obtain a first product deposited with the carbon nano tube.
(3) Carrying out acid passivation treatment on the first product; specifically, the first product is soaked in a mixed solution of nitric acid and hydrochloric acid for 4 hours, and then is sequentially washed, dehydrated and dried.
(4) Carrying out high-temperature chemical vapor deposition on the first product subjected to the acid passivation treatment and a silicon source under a protective atmosphere to obtain a second product deposited with nano-silicon; wherein the protective atmosphere is nitrogen, and the silicon source is tetrachlorosilane; specifically, the first product after acid passivation is placed into a rotary furnace, tetrachlorosilane is introduced at the flow rate of 6L/min in the nitrogen atmosphere with the flow rate of 120L/min and the environment of 500 ℃ for 1.5h, then nitrogen is introduced in the rotary furnace, and the rotary furnace is naturally cooled to room temperature, so that the second product deposited with nano-silicon is obtained.
(5) And carrying out high-temperature chemical vapor deposition on the second product and a carbon source under a protective atmosphere to form a carbon coating layer, thereby obtaining the composite material. Wherein the protective atmosphere is nitrogen atmosphere, and the carbon source in the step is acetylene; specifically, the second product is placed into a rotary furnace, acetylene is introduced at the flow rate of 1L/min in the nitrogen atmosphere with the flow rate of 50L/min and the environment of 700 ℃, the duration is 0.5h, then nitrogen introduction is switched, natural cooling is carried out to the room temperature, and classification and sieving treatment are sequentially carried out, so that the composite material with the particle size of 1-60 mu m can be obtained.
Example 2
The embodiment provides a composite material and a preparation method thereof, and particularly the preparation method of the composite material comprises the following steps:
(1) 10g of molecular formula Ti2Placing MXene of C into a reaction container, starting a vacuum pump to enable the vacuum degree of the reaction container to reach 0.05MPa, and then closing the vacuum pump; then 1L of ferric nitrate solution with the molar concentration of 3mol/L is added into a reaction vessel according to the speed of 30mL/min, stirred for 60min at the rotating speed of 200r/min, and then dried for 4h at the temperature of 120 ℃ to obtain MXene particles loaded with transition metal salt.
(2) And (2) placing the MXene particles loaded with the transition metal salt in a rotary furnace, introducing methane at the flow rate of 5L/min in an argon atmosphere with the flow rate of 100L/min and an environment with the temperature of 800 ℃ for 1h to generate the carbon nano tube, switching to introducing argon, and naturally cooling to room temperature to obtain a first product deposited with the carbon nano tube.
(3) And soaking the first product in nitric acid for 6 hours, and then sequentially carrying out cleaning, dehydration and drying treatment.
(4) And (3) putting the first product subjected to acid passivation treatment into a rotary furnace, introducing methyl trichlorosilane at the flow rate of 1L/min in an argon atmosphere with the flow rate of 200L/min and an environment at 800 ℃, continuing for 4 hours, switching to introducing argon, and naturally cooling to room temperature to obtain a second product deposited with nano silicon.
(5) And (3) putting the second product into a rotary furnace, introducing methane at the flow rate of 1L/min under the argon atmosphere with the flow rate of 100L/min and the environment of 800 ℃, continuing for 2 hours, switching to introducing argon, naturally cooling to room temperature, and sequentially carrying out grading and sieving treatment to obtain the composite material with the particle size of 1-60 mu m.
Example 3
The embodiment provides a composite material and a preparation method thereof, and particularly the preparation method of the composite material comprises the following steps:
(1) 10g of molecular formula Ti4C3Placing MXene into a reaction container, starting a vacuum pump to enable the vacuum degree of the reaction container to reach 0.06MPa, and then closing the vacuum pump; then adding 1L of nickel nitrate solution with the molar concentration of 2mol/L into a reaction container at the speed of 25mL/min, stirring at the rotating speed of 100r/min for 60min, and drying at the temperature of 100 ℃ for 4h to obtain MXene particles loaded with transition metal salts.
(2) And (2) placing the MXene particles loaded with the transition metal salt in a rotary furnace, introducing ethane at the flow rate of 1L/min in a nitrogen atmosphere at the flow rate of 50L/min and at the temperature of 600 ℃ for 2 hours to generate the carbon nano tube, switching to introduce nitrogen, and naturally cooling to room temperature to obtain a first product deposited with the carbon nano tube.
(3) And soaking the first product in nitric acid for 6 hours, and then sequentially carrying out cleaning, dehydration and drying treatment.
(4) And (3) putting the first product subjected to acid passivation into a rotary furnace, introducing tetrachlorosilane at the flow rate of 3L/min in a nitrogen atmosphere at the flow rate of 150L/min and at the temperature of 600 ℃ for 2 hours, switching to introducing nitrogen, and naturally cooling to room temperature to obtain a second product deposited with nano-silicon.
(5) And putting the second product into a rotary furnace, introducing ethane at the flow rate of 0.5L/min for 0.5h under the nitrogen atmosphere with the flow rate of 50L/min and the environment of 700 ℃, switching to introducing nitrogen, naturally cooling to room temperature, and sequentially carrying out grading and sieving treatment to obtain a third product with the particle size of 1-60 mu m and deposited with a carbon coating layer.
(6) Mixing 10g of the third product with 10g of a carbon material with the particle size of 1-60 mu m to obtain the composite material; wherein the carbon material is artificial graphite.
Example 4
The embodiment provides a composite material and a preparation method thereof, and particularly the preparation method of the composite material comprises the following steps:
(1) 10g of molecular formula Ti4C3Placing MXene into a reaction container, starting a vacuum pump to enable the vacuum degree of the reaction container to reach 0.06MPa, and then closing the vacuum pump; then adding 1L of ferric nitrate solution with the molar concentration of 0.5mol/L into a reaction vessel at the speed of 40mL/min, stirring at the rotating speed of 80r/min for 30min, and then drying at the temperature of 80 ℃ for 6h to obtain MXene particles loaded with transition metal salt.
(2) And (2) placing the MXene particles loaded with the transition metal salt in a rotary furnace, introducing ethane at the flow rate of 10L/min in the mixed atmosphere of argon and nitrogen at the flow rate of 100L/min and the environment at 800 ℃ for 3 hours to generate the carbon nano tube, switching to introducing argon and nitrogen, and naturally cooling to room temperature to obtain a first product deposited with the carbon nano tube.
(3) And soaking the first product in nitric acid for 4 hours, and then sequentially carrying out cleaning, dehydration and drying treatment.
(4) And (3) putting the first product subjected to acid passivation into a rotary furnace, introducing tetrachlorosilane at the flow rate of 2L/min in the mixed atmosphere of argon and nitrogen at the flow rate of 200L/min and in the environment of 500 ℃, continuing for 3.5h, switching to introducing argon and nitrogen, and naturally cooling to room temperature to obtain a second product deposited with nano-silicon.
(5) And putting the second product into a rotary furnace, introducing methane at the flow rate of 1L/min under the mixed atmosphere of argon and nitrogen at the flow rate of 100L/min and the environment of 800 ℃, continuing for 0.5h, switching to introducing the argon and the nitrogen, naturally cooling to room temperature, and sequentially carrying out grading and sieving treatment to obtain a third product with the particle size of 1-60 mu m and deposited with a carbon coating layer.
(6) Mixing 10g of the third product with 6g of carbon material with the particle size of 1-60 mu m to obtain the composite material; wherein the carbon material is artificial graphite.
Example 5
The embodiment provides a composite material and a preparation method thereof, and particularly the preparation method of the composite material comprises the following steps:
(1) 10g of molecular formula Ti4C3Placing MXene into a reaction container, starting a vacuum pump to enable the vacuum degree of the reaction container to reach 0.06MPa, and then closing the vacuum pump; then 1L of ferric nitrate solution with the molar concentration of 4mol/L is added into a reaction vessel according to the speed of 10mL/min, stirred for 60min at the rotating speed of 200r/min, and then dried for 8h at the temperature of 100 ℃ to obtain MXene particles loaded with transition metal salt.
(2) And (2) placing the MXene particles loaded with the transition metal salt in a rotary furnace, introducing ethane at the flow rate of 1L/min in a nitrogen atmosphere at the flow rate of 200L/min and an environment at 800 ℃ for 1h to generate the carbon nano tube, switching to introduce nitrogen, and naturally cooling to room temperature to obtain a first product deposited with the carbon nano tube.
(3) And soaking the first product in sulfuric acid for 8 hours, and then sequentially carrying out cleaning, dehydration and drying treatment.
(4) And (3) putting the first product subjected to acid passivation into a rotary furnace, introducing tetrachlorosilane at the flow rate of 2L/min in a nitrogen atmosphere with the flow rate of 200L/min and at the temperature of 600 ℃, continuing for 1h, switching to introducing nitrogen, and naturally cooling to room temperature to obtain a second product deposited with nano-silicon.
(5) And putting the second product into a rotary furnace, introducing ethane at the flow rate of 1L/min for 0.5h under the nitrogen atmosphere with the flow rate of 100L/min and the environment of 700 ℃, switching to introducing nitrogen, naturally cooling to room temperature, and sequentially carrying out grading and sieving treatment to obtain a third product with the particle size of 1-60 mu m and deposited with a carbon coating layer.
(6) Mixing 10g of the third product with 50g of carbon material with the particle size of 1-60 mu m to obtain the composite material; wherein the carbon material is natural graphite.
Example 6
This example provides a composite material and a method for preparing the same, and specifically, the method for preparing the composite material is different from the method for preparing the composite material provided in example 5 in that: in the step (1), cobalt chloride solution is used for replacing ferric nitrate solution; in step (2), a mixture of ethylene and propane is used instead of ethane; in the step (4), a mixture of monochlorosilane and dichlorosilane is used to replace tetrachlorosilane; in step (5), a mixture of propane and n-butane is used instead of ethane; in the step (6), the mixture of mesocarbon microbeads and soft carbon is used for replacing natural graphite; the process other than this difference was the same as that of example 5.
Example 7
This example provides a composite material and a method for preparing the same, and specifically, the method for preparing the composite material is different from the method for preparing the composite material provided in example 5 in that: in the step (1), a mixed solution of chromium sulfate, ferric nitrate and ferric oxalate is used for replacing a ferric nitrate solution; in the step (2), a mixture of acetylene, ethylene and methane is used instead of ethane; in the step (4), trichlorosilane, tetrachlorosilane and a mixture of monomethyl trichlorosilane are used to replace tetrachlorosilane; in step (5), a mixture of ethane, propane and n-butane is used instead of ethane; in the step (6), the mixture of mesocarbon microbeads, soft carbon and hard carbon is used for replacing natural graphite; the process other than this difference was the same as that of example 5.
Example 8
This example provides a composite material and a method for preparing the same, and specifically, the method for preparing the composite material is different from the method for preparing the composite material provided in example 5 in that: in the step (1), a mixed solution of ferric nitrate and ferric oxalate is used for replacing a ferric nitrate solution; in the step (2), a mixture of acetylene and ethylene is used instead of ethane; in the step (4), a mixture of dimethyl trichlorosilane and trimethylchlorosilane is used for replacing tetrachlorosilane; in the step (5), a mixture of methane and ethane is used instead of ethane; in the step (6), the mesocarbon microbeads are used for replacing natural graphite; the process other than this difference was the same as that of example 5.
Example 9
This embodiment provides an electrode, the method of making the electrode comprising the steps of:
(1) placing the composite material provided in the embodiment 1, polyvinylidene fluoride and conductive graphite in a high-speed dispersion machine for stirring and mixing to obtain active slurry; wherein the mass ratio of the composite material to the polyvinylidene fluoride to the conductive graphite is 90:6: 4.
(2) And coating the active slurry on an aluminum foil to obtain the electrode. The electrode can be used as a negative electrode of a lithium ion battery.
Example 10
This embodiment provides an electrode, the method of making the electrode comprising the steps of:
(1) placing the composite material provided in the embodiment 2, polyvinylidene fluoride and conductive graphite in a high-speed dispersion machine for stirring and mixing to obtain active slurry; wherein the mass ratio of the composite material to the polyvinylidene fluoride to the conductive graphite is 95:4: 1.
(2) And coating the active slurry on an aluminum foil to obtain the electrode. The electrode can be used as a negative electrode of a lithium ion battery.
Example 11
This embodiment provides an electrode, the method of making the electrode comprising the steps of:
(1) placing the composite material provided in the embodiment 3, polyvinylidene fluoride and conductive graphite in a high-speed dispersion machine for stirring and mixing to obtain active slurry; wherein the mass ratio of the composite material to the polyvinylidene fluoride to the conductive graphite is 93:5: 2.
(2) And coating the active slurry on an aluminum foil to obtain the electrode. The electrode can be used as a negative electrode of a lithium ion battery.
Example 12
This embodiment provides an electrode, the method of making the electrode comprising the steps of:
(1) placing the composite material provided in the embodiment 4, polyvinylidene fluoride and conductive graphite in a high-speed dispersion machine for stirring and mixing to obtain active slurry; wherein the mass ratio of the composite material to the polyvinylidene fluoride to the conductive graphite is 93:5: 2.
(2) And coating the active slurry on an aluminum foil to obtain the electrode. The electrode can be used as a negative electrode of a lithium ion battery.
Example 13
This embodiment provides an electrode, the method of making the electrode comprising the steps of:
(1) placing the composite material provided in the embodiment 5, polyvinylidene fluoride and conductive graphite in a high-speed dispersion machine for stirring and mixing to obtain active slurry; wherein the mass ratio of the composite material to the polyvinylidene fluoride to the conductive graphite is 93:5: 2.
(2) And coating the active slurry on an aluminum foil to obtain the electrode. The electrode can be used as a negative electrode of a lithium ion battery.
The electrodes provided in the above examples 9 to 13 were used as negative electrodes, respectively, and assembled with lithium positive electrodes to make 5 groups of lithium ion batteries; the 5 groups of lithium ion batteries are respectively tested for the performances of the first discharge capacity, the first coulombic efficiency, the cycle capacity retention rate and the like under different multiplying factors, and the test results are shown in table 1.
TABLE 1
As can be seen from table 1 above, when the composite material provided by the embodiment of the present invention is used as a negative electrode material of a lithium ion battery, the charge and discharge rate, the rate capability, and the cycle life of the battery can be improved.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A preparation method of a composite material is characterized by comprising the following steps:
(1) mixing MXene and a transition metal salt solution under a vacuum condition, and then sequentially filtering and drying to obtain MXene particles loaded with the transition metal salt;
(2) carrying out high-temperature chemical vapor deposition on MXene particles loaded with transition metal salts and a carbon source under a protective atmosphere to obtain a first product deposited with carbon nanotubes;
(3) carrying out acid passivation treatment on the first product;
(4) carrying out high-temperature chemical vapor deposition on the first product subjected to the acid passivation treatment and a silicon source under a protective atmosphere to obtain a second product deposited with nano-silicon;
(5) and carrying out high-temperature chemical vapor deposition on the second product and a carbon source under a protective atmosphere to form a carbon coating layer, thereby obtaining the composite material.
2. The method for preparing a composite material according to claim 1, wherein the transition metal salt solution is one or more of a nitrate solution, a chloride solution, a sulfate solution and an oxalate solution of the transition metal; the transition metal is one or more of iron, cobalt, nickel and chromium.
3. The method of claim 1, wherein in steps (2) and (5), the carbon source is one or more of acetylene, ethylene, methane, ethane, propane, and n-butane.
4. The method according to claim 1, wherein in the step (4), the silicon source is one or more of monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, monomethyltrichlorosilane, dimethyltrichlorosilane, and trimethylmonochlorosilane.
5. The method for preparing a composite material according to claim 1, wherein the step (5) comprises the following steps:
carrying out high-temperature chemical vapor deposition on the second product and a carbon source under a protective atmosphere to obtain a third product deposited with a carbon coating layer;
mixing the third product with a carbon material to obtain the composite material; the carbon material is one or more of natural graphite, artificial graphite, mesocarbon microbeads, soft carbon and hard carbon.
6. A composite material prepared by the preparation method of any one of claims 1 to 5.
7. Use of the composite material according to claim 6 as a battery material.
8. An electrode, wherein the composite material of claim 6 is partially or completely coated on the electrode.
9. An electrode according to claim 8, wherein the method of making the electrode comprises the steps of:
mixing the composite material with polyvinylidene fluoride and conductive graphite to obtain active slurry; the mass ratio of the composite material to the polyvinylidene fluoride to the conductive graphite is (90-95): (4-6): 1-4);
and coating the active slurry on a metal foil to obtain the electrode.
10. A lithium ion battery comprising an electrode according to claim 8 or 9.
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| PCT/CN2020/110557 WO2021077884A1 (en) | 2019-10-23 | 2020-08-21 | Composite material, preparation method therefor and use thereof as electrode material |
| ZA2021/05317A ZA202105317B (en) | 2019-10-23 | 2021-07-27 | Composite material, its preparation method, and its use as electrode material |
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| CN112038641A (en) * | 2020-09-09 | 2020-12-04 | 宁波富理电池材料科技有限公司 | MXene silicon-carbon composite material, preparation method thereof, negative electrode and lithium ion battery |
| WO2021077884A1 (en) * | 2019-10-23 | 2021-04-29 | 广东海洋大学 | Composite material, preparation method therefor and use thereof as electrode material |
| CN113066965A (en) * | 2021-03-22 | 2021-07-02 | 宁波杉杉新材料科技有限公司 | MXene-silicon composite anode material, battery containing MXene-silicon composite anode material, and preparation method and application of MXene-silicon composite anode material |
| WO2021172415A1 (en) * | 2020-02-26 | 2021-09-02 | Murata Manufacturing Co., Ltd. | Paste and conductive film and their production methods |
| WO2022205154A1 (en) * | 2021-03-31 | 2022-10-06 | 宁德新能源科技有限公司 | Negative electrode active material, electrochemical apparatus, and electronic apparatus |
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| CN110752364B (en) | 2021-10-01 |
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