CN111092210B - Ternary positive electrode composite material and preparation method and application thereof - Google Patents

Ternary positive electrode composite material and preparation method and application thereof Download PDF

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CN111092210B
CN111092210B CN201911400301.2A CN201911400301A CN111092210B CN 111092210 B CN111092210 B CN 111092210B CN 201911400301 A CN201911400301 A CN 201911400301A CN 111092210 B CN111092210 B CN 111092210B
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graphene
positive electrode
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CN111092210A (en
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谭强强
徐宇兴
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Langfang green industry technology service center
Institute of Process Engineering of CAS
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Langfang Institute of Process Engineering of CAS
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Abstract

The invention discloses a ternary cathode composite material and a preparation method and application thereof, wherein the composite material comprises a ternary cathode material core and a shell coated on the surface of the core, and the shell comprises a first coating and a second coating; the first cladding is a three-dimensional nano-network layered structure and comprises a conductive polymer/graphene/carbon nano tube compound, and a hydrogen-containing lithium titanium oxide and FeF (FeF) dispersed on the surface of the compound in situ3(H2O)0.33And the second coating is a carbonized product of polyvinyl alcohol. The lithium ion battery prepared by the ternary cathode composite material has high ionic conductivity and electronic conductivity, and has the outstanding advantages of high discharge specific capacity, high first coulombic efficiency, high cycling stability and the like.

Description

Ternary positive electrode composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrochemical power supply material preparation, particularly belongs to the technical field of lithium ion secondary battery anode material preparation, and relates to a ternary anode composite material and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high working voltage, good cycling stability, environmental friendliness and the like, and is widely applied to the fields of electric automobiles, notebook computers, mobile phones and the like. The cathode material is used as a key material in the lithium ion battery and plays an important role in the performance of the battery. Compared with other anode materials, the ternary material has the advantages of high specific capacity, low preparation cost and the like, and has good commercial application prospect. However, the ternary material has the problems of ion mixed discharge and excessive surface alkali residue in the application process, and the prior art generally adopts a water washing method to remove the surface alkali residue, but if the water washing is not thorough, the surface alkali residue cannot be effectively reduced, and if the water washing frequency is too many, the problems of particle breakage and the like are caused, so that the performance of the product performance is influenced.
CN108134069A discloses a composite modification method of a cathode material, which comprises the following steps: 1) removing impurities from the precursor of the positive electrode material to obtain a precursor of the positive electrode material after cleaning and removing impurities; 2) mixing the cleaned and impurity-removed precursor of the positive electrode material with a lithium source; 3) sintering to obtain a positive electrode material substrate; 4) dispersing a source substance of a coating material and a coating auxiliary agent into a solvent for dissolving to obtain a dispersion system, adding a positive electrode material matrix into the dispersion system, stirring, then carrying out solid-liquid separation to obtain a coated solid substance, and finally carrying out heat treatment to obtain a material with a coating material layer; 5) and washing and drying the obtained material to obtain the composite modified lithium ion battery anode material. The method can prepare the high-nickel anode material with better stability, and after washing, the structure is kept stable, the residual alkali is effectively reduced, and the performance is not deteriorated. However, the process for reducing the residual alkali through water washing is complex, a large amount of water resource is wasted, the discharge of washing water can cause certain pressure on environmental protection, and if the washing process is not properly processed, the surface structure of the anode material is damaged in different degrees due to repeated washing, so that the electrochemical performance of the material can be influenced.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a ternary cathode composite material, and a preparation method and use thereof. The lithium ion battery prepared by the ternary cathode composite material has high ionic conductivity and electronic conductivity, and has the outstanding advantages of high discharge specific capacity, high first coulombic efficiency, high cycling stability and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a ternary cathode composite material, which comprises a ternary cathode material core and a shell coated on the surface of the core, wherein the shell comprises a first coating and a second coating;
the first cladding is a three-dimensional nano-network layered structure and comprises a conductive polymer/graphene/carbon nano tube compound, and a hydrogen-containing lithium titanium oxide and FeF (FeF) dispersed on the surface of the compound in situ3(H2O)0.33And the second coating is a carbonized product of polyvinyl alcohol.
The invention adopts a conductive polymer/graphene/carbon nano tube compound, a hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The three-dimensional nano-network laminated structure composite material formed by in-situ polymerization is matched with a carbonized product (especially quantum dots) of polyvinyl alcohol to coat the ternary cathode material to obtain the ternary cathode composite material with the core-shell structure.
Preferably, the ternary positive electrode material core comprises any one or a combination of two of nickel cobalt lithium manganate or nickel cobalt lithium aluminate.
Preferably, the molar ratio of nickel, cobalt and manganese in the nickel cobalt lithium manganate is Ni: Co: Mn ═ 4-9: 1-3: 2-3, such as 7:1:1, 8:1:1, 9:1:1, 6:2:2, 5:3:2 or 4:3:3, and the like.
Preferably, the molar ratio of nickel, cobalt and aluminum in the nickel cobalt lithium aluminate is Ni: Co: Al (7-9):1:1, for example, 7:1:1, 7.5:1:1, 8:1:1, 9:1:1, etc.
Preferably, the shell has a thickness of 1nm to 50nm, such as 1nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm or 50nm, etc., preferably 2nm to 30 nm.
Preferably, the mass percentage of the first coating is 0.01% to 20%, for example, 0.01%, 0.05%, 0.1%, 0.3%, 0.5%, 1%, 2%, 5%, 10%, 15%, 16%, 17%, 18%, 20%, or the like, preferably 0.1% to 15%, and more preferably 0.5% to 10%, based on 100% of the total mass of the ternary positive electrode composite material.
Preferably, the carbonization product of the polyvinyl alcohol is a carbon quantum dot.
Preferably, in the first coating, the conductive polymer/graphene/carbon nanotube composite, the hydrogen-containing lithium titanium oxide and the FeF3(H2O)0.33The mass ratio of (6-9.4): (0.5-3): (0.1-1), for example 6:3:1, 7:2:0.1, 9:0.5:0.5, 8:1.5:0.5, 7:2.5:0.5, 9:0.2:0.8 or 8.5:0.5: 1.
Preferably, in the conductive polymer/graphene/carbon nanotube composite, the mass ratio of the conductive polymer to the graphene to the carbon nanotubes is (0.1-2): (0.1-3): (0.5-5), such as 1:2:0.5, 0.5:2:1.5, 1.5:0.5:2.8, 1.6:1.5:3.6 or 1.8:2.5: 4.3.
Preferably, the conductive polymer in the conductive polymer/graphene/carbon nanotube composite includes any one of polypyrrole, polyaniline, polythiophene or polyoxyethylene, a mixture of at least two of them, or a copolymer formed by monomers of at least two of the conductive polymers.
Preferably, the graphene in the conductive polymer/graphene/carbon nanotube composite is formed by chemically reducing graphene oxide.
Preferably, the carbon nanotubes in the conductive polymer/graphene/carbon nanotube composite are single-walled carbon nanotubes or multi-walled carbon nanotubes, or a combination of the two, preferably multi-walled carbon nanotubes.
Preferably, the hydrogen-containing lithium titanium oxide compound is: a compound formed by four elements of Li, H, Ti and O in any proportion;
preferably, the hydrogen-containing lithium titanium oxide compound is: li is simultaneously present in any proportion in the phase structure4Ti5O12、TiO2And HxTiyOzPreferably a compound of (a) in a substance phaseIn which Li is present simultaneously in any proportion4Ti5O12And H2Ti3O7·(H2O·3TiO2) Wherein x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 3, and z is more than 0 and less than or equal to 7;
preferably, the hydrogen-containing lithium titanium oxide compound is: li1.81H0.19Ti2O5·aH2O, wherein a > 0.
In a second aspect, the present invention provides a method for preparing a ternary positive electrode composite material according to the first aspect, the method comprising the steps of:
(1) preparing a solution A from a polyvinyl alcohol (PVA) solvent;
(2) adding the first coating into the solution A obtained in the step (1), and uniformly stirring to obtain a solution B;
(3) adding a ternary cathode material into the solution B obtained in the step (2) to obtain slurry C;
(4) under the atmosphere of air or oxygen, carrying out microwave treatment on the slurry C at the temperature of 300-500 ℃ to obtain a ternary cathode composite material;
the first cladding is a three-dimensional nano-network layered structure and comprises a conductive polymer/graphene/carbon nano tube compound, and a hydrogen-containing lithium titanium oxide and FeF (FeF) dispersed on the surface of the compound in situ3(H2O)0.33。
Preparing a polyvinyl alcohol solution with certain viscosity, adding a first coating into the solution to obtain a coating solution, coating and modifying a ternary cathode material by adopting a liquid phase coating method, and performing microwave treatment in the air or oxygen atmosphere to pyrolyze polyvinyl alcohol into carbon quantum dots by microwave, wherein the carbon quantum dots are uniformly distributed by combining the liquid phase coating modification method and an in-situ pyrolysis method; and the microwave temperature is low, so that the ternary cathode material is not reduced, the specific three-dimensional nano network layered structure of the first coating material is not damaged, and the coating effect is not influenced.
Preferably, the polyvinyl alcohol is used in an amount of 0.1% to 5%, for example, 0.2%, 0.3%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%, preferably 0.5% to 2%, based on 100% of the total mass of the ternary positive electrode composite material prepared.
Preferably, the solvent of step (1) comprises water and/or ethanol.
Preferably, the first coating in step (2) is prepared from a conductive polymer/graphene/carbon nanotube composite, a hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33A composite material prepared by in situ polymerization.
Preferably, the first coating in step (2) is prepared by the following method:
(a) mixing graphene oxide with a surfactant, performing ultrasonic dispersion, mixing with a reducing agent, and performing chemical reduction to obtain reduced graphene forming micelles between graphene layers;
(b) dispersing the reduced graphene in the step (a) in a solvent, carrying out ultrasonic treatment, adding a conductive polymer monomer, continuing ultrasonic treatment, and adding an initiator, a carbon nano tube, a hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33And carrying out polymerization reaction to obtain the coating material.
Alternatively, the first coating in the step (2) is prepared by the following method:
firstly, mixing graphene oxide with a surfactant, performing ultrasonic dispersion, then mixing the graphene oxide with carbon nanotubes and a reducing agent, and performing chemical reduction to obtain a mixture of reduced graphene with micelles formed between graphene layers and carbon nanotubes with micelles formed on the surfaces;
dispersing the mixture obtained in the step one in a solvent, performing ultrasonic treatment, adding a conductive polymer monomer, continuing the ultrasonic treatment, and adding an initiator, a hydrogen-containing lithium titanium oxide compound and FeF3(H2O)0.33And carrying out polymerization reaction at 40 ℃ to obtain the coating material.
Preferably, the mass ratio of the graphene oxide to the reducing agent in the step (a) and the step (r) is 1 (1-2), for example, 1:1.2, 1:1.5, or 1:1.8, and more preferably 1 (1-1.5).
Preferably, the chemical reduction in step (a) and step (r) is carried out in a water bath at 75 ℃ to 95 ℃, e.g., 80 ℃, 85 ℃, or 90 ℃, etc.
Preferably, the ultrasonic power in step (a) and step (r) is 50W-600W, such as 100W, 200W, 300W, 400W or 500W.
Preferably, in the step (a) and the step (r), the mass ratio of the graphene oxide to the surfactant is independently 1 (0.1-2), for example 1:0.3, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5 or 1:1.8, and the like, and is preferably 1 (0.3-1.5).
Preferably, the reducing agents in step (a) and step (r) independently comprise any one or a combination of two of sodium borohydride or hydrazine hydrate, preferably hydrazine hydrate.
Preferably, the solvent in step (b) and step (c) comprises any one or a mixture of at least two of ethanol, deionized water, inorganic protonic acid or chloroform solution of ferric chloride.
Preferably, the power of the ultrasound in the step (b) and the step (c) is 80W-500W, such as 100W, 200W, 300W or 400W.
Preferably, the time for continuing the ultrasound in the step (b) and the step (c) is independently 30min-2h, such as 40min, 60min, 80min or 100 min.
Preferably, in step (b) and step (c), the initiator is ammonium persulfate.
Preferably, in step (b) and step (c), the amount of initiator added is independently 0.1 to 2 times, for example 0.3, 0.5, 0.8, 1, 1.2, 1.5 or 1.8 times, etc., preferably 0.5 to 1.5 times the mass of polymer monomer added.
Preferably, the polymerization reaction of steps (b) and (c) is carried out in an ice-water bath, the temperature of which is known to the person skilled in the art to be 0 ℃.
Preferably, the polymerization in step (b) and step (c) is carried out with stirring at a rate of 500r/min to 3000r/min, such as 3000r/min, 650r/min, 800r/min, 1000r/min, 1250r/min, 1500r/min, 1700r/min, 1850r/min, 2000r/min, 2300r/min, 2500r/min, 2800r/min or 3000 r/min.
Preferably, the polymerization reaction time in step (b) and step (c) is independently 12h to 30h, such as 15h, 18h, 20h, 22h, 25h or 28h, etc.
Preferably, the carbon nanotubes of step (b) and step (r) are independently single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
Preferably, the carbon nanotubes of steps (b) and (c) are hydroxylated carbon nanotubes, preferably hydroxylated multi-walled carbon nanotubes.
Preferably, the method further comprises the step of separating and removing the surplus surfactant after the chemical reduction in the steps (a) and (r).
Preferably, the method further comprises the steps of separating and drying after the polymerization reaction of the steps (b) and (c), preferably, the drying is performed at 50 ℃ to 70 ℃, for example, 55 ℃, 60 ℃, or 65 ℃, etc., and vacuum drying is performed.
As a preferable technical scheme of the method, the ternary cathode material in the step (3) comprises any one or a combination of two of nickel cobalt lithium manganate or nickel cobalt lithium aluminate.
Preferably, the solid content of the slurry C in the step (3) is 20% to 70%, such as 25%, 35%, 40%, 50%, 60%, 65%, or 70%, etc., preferably 30% to 60%.
Preferably, the temperature of the microwave treatment in the step (3) is 350-450 ℃. For example, 350 ℃, 375 ℃, 400 ℃, 430 ℃, 440 ℃, or 450 ℃.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) dissolving polyvinyl alcohol (PVA) in water and/or ethanol to prepare a solution A;
(2) adding the first coating into the solution A obtained in the step (1), and uniformly stirring to obtain a solution B;
(3) adding a ternary cathode material into the solution B obtained in the step (2) to obtain slurry C, wherein the solid content of the slurry C is 20-70%;
(4) under the atmosphere of air or oxygen, carrying out microwave treatment on the slurry C at the temperature of 300-500 ℃ to obtain a ternary cathode composite material;
the first cladding is a three-dimensional nano-network layered structure and comprises a conductive polymer/graphene/carbon nano tube compound, and a hydrogen-containing lithium titanium oxide and FeF (FeF) dispersed on the surface of the compound in situ3(H2O)0.33；
The usage amount of the polyvinyl alcohol is 0.1-5% based on the total mass of the prepared ternary cathode composite material as 100%.
In a third aspect, the present invention provides a use of the ternary cathode composite material according to the first aspect, wherein the cathode material is used in a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts a conductive polymer/graphene/carbon nano tube compound, a hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The three-dimensional nano-network laminated structure composite material formed by in-situ polymerization is matched with a carbonized product (especially quantum dots) of polyvinyl alcohol to coat the ternary cathode material to obtain the ternary cathode composite material with the core-shell structure.
(2) Preparing a polyvinyl alcohol solution with certain viscosity, adding a first coating into the solution to obtain a coating solution, coating and modifying a ternary cathode material by adopting a liquid phase coating method, and performing microwave treatment in the air or oxygen atmosphere to pyrolyze polyvinyl alcohol into carbon quantum dots by microwave, wherein the carbon quantum dots are uniformly distributed by combining the liquid phase coating modification method and an in-situ pyrolysis method; and the microwave temperature is low, so that the ternary cathode material is not reduced, the specific three-dimensional nano network layered structure of the first coating material is not damaged, and the coating effect is not influenced.
(3) According to the invention, the first coating with the three-dimensional nano-network layered structure and the carbonized product of polyvinyl alcohol are introduced as the second coating, and a water washing process is not needed, so that more lithium ion transmission channels can be provided while the residual alkali on the surface of the anode material is reduced, the electronic conductivity, the ionic conductivity and the cycle stability of the ternary anode material are greatly improved, and the ternary anode material has a wider application prospect and a wider practical application value.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
In the cathode material of this embodiment, the ternary cathode material is nickel cobalt lithium manganate, the molar ratio of nickel to cobalt to manganese is Ni to Co to Mn is 7 to 1, the mass percentage content of the first coating is 10%, the second coating is a carbonized product of polyvinyl alcohol, the usage amount of the polyvinyl alcohol is 0.1%,
in the first coating, a conductive polymer/graphene/carbon nanotube composite, a hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The mass ratio of (A) to (B) is 6:3: 1; the mass ratio of the conductive polymer to the graphene to the carbon nanotubes in the conductive polymer/graphene/carbon nanotube composite is 1:1.5: 1.5;
the preparation method of the cathode material comprises the following steps:
(1) dissolving polyvinyl alcohol (PVA) in water to prepare a solution A;
(2) adding the first coating into the solution A obtained in the step (1), and uniformly stirring to obtain a solution B;
(3) adding a ternary cathode material into the solution B obtained in the step (2) to obtain slurry C, wherein the solid content of the slurry C is 60%;
(4) under the air atmosphere, carrying out microwave treatment on the slurry C at 375 ℃ to obtain a ternary cathode composite material;
the first cladding is a three-dimensional nano-network layered structure and comprises a conductive polymer/graphene/carbon nano-tube compound and hydrogen-containing lithium dispersed on the surface of the compound in situTitanium oxide and FeF3(H2O)0.33The preparation method comprises the following steps:
(a) adding a proper amount of hexadecyl trimethyl ammonium bromide powder into a graphene oxide dispersion liquid to enable the mass ratio of graphene oxide to hexadecyl trimethyl ammonium bromide to be 1:0.1, fully dispersing the graphene oxide and the hexadecyl trimethyl ammonium bromide through ultrasonic waves under the power of 50W, then adding hydrazine hydrate to enable the mass ratio of the graphene oxide to the hydrazine hydrate to be 1:2, carrying out chemical reduction in a water bath at the temperature of 75 ℃, forming micelles among graphene layers through a surfactant in the process that the graphene oxide is reduced by the hydrazine hydrate, and centrifugally separating a product to remove the redundant hexadecyl trimethyl ammonium bromide serving as the surfactant to obtain the reduced graphene with the micelles among the graphene layers.
(b) Dispersing the reduced graphene in ethanol, carrying out ultrasonic treatment for 5min under the power of 600W, then adding pyrrole monomer, continuing ultrasonic treatment for 30min, adding ammonium persulfate with the mass being 0.1 time of that of the pyrrole monomer, and adding a hydroxylated multi-walled carbon nanotube and a hydrogen-containing lithium titanium oxide Li according to the proportion1.81H0.19Ti2O5·H2O and FeF3(H2O)0.33Rapidly stirring at the speed of 500r/min in ice water bath at 0 ℃ for polymerization reaction for 30h, centrifugally separating the reaction product, and vacuum drying at 25 ℃ to obtain the conductive polymer/graphene/carbon nanotube composite, the hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The coating material with the three-dimensional nano-network layered structure is prepared by an in-situ polymerization method.
Example 2
In the cathode material of this embodiment, the ternary cathode material is nickel cobalt lithium manganate, the molar ratio of nickel to cobalt to manganese is Ni to Co to Mn is 6 to 2, the mass percentage content of the first coating is 0.5%, the second coating is a carbonized product of polyvinyl alcohol, the usage amount of the polyvinyl alcohol is 2%,
in the first coating, a conductive polymer/graphene/carbon nanotube composite, a hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The mass ratio of (1) to (2) is 7:2.5: 0.5; the mass ratio of the conductive polymer to the graphene to the carbon nanotubes in the conductive polymer/graphene/carbon nanotube composite is 0.2:3: 0.8;
(1) dissolving polyvinyl alcohol (PVA) in ethanol to prepare a solution A;
(2) adding the first coating into the solution A obtained in the step (1), and uniformly stirring to obtain a solution B;
(3) adding a ternary cathode material into the solution B obtained in the step (2) to obtain slurry C, wherein the solid content of the slurry C is 30%;
(4) under the air atmosphere, carrying out microwave treatment on the slurry C at 375 ℃ to obtain a ternary cathode composite material;
the first cladding is a three-dimensional nano-network layered structure and comprises a conductive polymer/graphene/carbon nano tube compound, and a hydrogen-containing lithium titanium oxide and FeF (FeF) dispersed on the surface of the compound in situ3(H2O)0.33The preparation method comprises the following steps:
(a) adding a proper amount of hexadecyl trimethyl ammonium bromide powder into a graphene oxide dispersion liquid to enable the mass ratio of graphene oxide to hexadecyl trimethyl ammonium bromide to be 1:2, fully dispersing the graphene oxide and the hexadecyl trimethyl ammonium bromide through ultrasonic waves under the power of 100W, then adding hydrazine hydrate to enable the mass ratio of the graphene oxide to the hydrazine hydrate to be 1:1, carrying out chemical reduction in a water bath at the temperature of 95 ℃, forming micelles among graphene layers through a surfactant in the process that the graphene oxide is reduced by the hydrazine hydrate, and centrifugally separating a product to remove the redundant hexadecyl trimethyl ammonium bromide serving as the surfactant to obtain the reduced graphene forming the micelles among the graphene layers.
(b) Dispersing the reduced graphene in a chloroform solution of ferric trichloride (the mass concentration is 30 percent), carrying out ultrasonic treatment for 3min under the power of 500W, then adding a thiophene monomer, continuing to carry out ultrasonic treatment for 2h, adding ammonium persulfate with the mass 2 times that of the thiophene monomer, adding a hydroxylated multi-walled carbon nanotube according to the proportion, wherein the phase structure of the multi-walled carbon nanotube simultaneously contains Li4Ti5O12And H2Ti3O7·(H2O·3TiO2) Hydrogen-containing lithium titaniumOxygen compound and FeF3(H2O)0.33Rapidly stirring at 3000 rpm in ice water bath at 0 deg.C for polymerization reaction for 12h, centrifuging the reaction product, and vacuum drying at 60 deg.C to obtain conductive polymer/graphene/carbon nanotube composite, hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The coating material with the three-dimensional nano-network layered structure is prepared by an in-situ polymerization method.
Example 3
In the cathode material of this embodiment, the ternary cathode material is nickel cobalt lithium manganate, the molar ratio of nickel to cobalt to manganese is Ni to Co to Mn is 5:3:2, the mass percentage content of the first coating is 15%, the second coating is a carbonized product of polyvinyl alcohol, the usage amount of the polyvinyl alcohol is 0.5%,
in the first coating, a conductive polymer/graphene/carbon nanotube composite, a hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The mass ratio of (A) to (B) is 9.4:0.5: 0.1; the mass ratio of the conductive polymer to the graphene to the carbon nanotubes in the conductive polymer/graphene/carbon nanotube composite is 2:0.1: 2.6;
the preparation method of the cathode material comprises the following steps:
(1) dissolving polyvinyl alcohol (PVA) in ethanol to prepare a solution A;
(2) adding the first coating into the solution A obtained in the step (1), and uniformly stirring to obtain a solution B;
(3) adding a ternary cathode material into the solution B obtained in the step (2) to obtain slurry C, wherein the solid content of the slurry C is 35%;
(4) under the air atmosphere, carrying out microwave treatment on the slurry C at the temperature of 500 ℃ to obtain a ternary cathode composite material;
the first cladding is a three-dimensional nano-network layered structure and comprises a conductive polymer/graphene/carbon nano tube compound, and a hydrogen-containing lithium titanium oxide and FeF (FeF) dispersed on the surface of the compound in situ3(H2O)0.33The preparation method comprises the following steps:
(a) adding a proper amount of sodium dodecyl sulfate into the graphene oxide dispersion liquid to enable the mass ratio of the graphene oxide to the sodium dodecyl sulfate to be 1:0.5, fully dispersing the graphene oxide and the sodium dodecyl sulfate through ultrasonic waves under the power of 300W, then adding sodium borohydride to enable the mass ratio of the graphene oxide to the sodium borohydride to be 1:1.5, carrying out chemical reduction in a water bath at the temperature of 80 ℃, forming micelles among graphene layers through a surfactant in the process that the graphene oxide is reduced by the sodium borohydride, and centrifugally separating a product to remove the redundant sodium dodecyl sulfate serving as the surfactant to obtain the reduced graphene with the micelles formed among the graphene layers.
(b) Dispersing the reduced graphene in chloroform, carrying out ultrasonic treatment for 8min under the power of 200W, adding an aniline monomer, continuing ultrasonic treatment for 2h, adding ammonium persulfate with the mass being 0.5 time that of the aniline monomer, adding a hydroxylated multi-walled carbon nanotube according to the proportion, and simultaneously containing Li in a phase structure1.81H0.19Ti2O5·H2O and H2Ti3O7·(H2O·3TiO2) With hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33Rapidly stirring in ice water bath at 0 ℃ at a speed of 2000r/min for carrying out polymerization reaction for 15h, centrifugally separating the reaction product, and drying in vacuum at 60 ℃ to obtain the conductive polymer/graphene/carbon nanotube composite, the hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The coating material with the three-dimensional nano-network layered structure is prepared by an in-situ polymerization method.
Example 4
In the cathode material of this embodiment, the ternary cathode material is nickel cobalt lithium aluminate, the molar ratio of nickel to cobalt to aluminum is Ni to Co to Mn is 8.5 to 1, the mass percentage of the first coating is 18%, the second coating is a carbonized product of polyvinyl alcohol, the usage amount of the polyvinyl alcohol is 1.5%,
in the first coating, a conductive polymer/graphene/carbon nanotube composite, a hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33In a mass ratio of8.5:1: 0.5; the mass ratio of the conductive polymer to the graphene to the carbon nanotubes in the conductive polymer/graphene/carbon nanotube composite is 1.5:2: 4.8;
the preparation method of the cathode material comprises the following steps:
(1) dissolving polyvinyl alcohol (PVA) in water to prepare a solution A;
(2) adding the first coating into the solution A obtained in the step (1), and uniformly stirring to obtain a solution B;
(3) adding a ternary cathode material into the solution B obtained in the step (2) to obtain slurry C, wherein the solid content of the slurry C is 20%;
(4) under the oxygen atmosphere, carrying out microwave treatment on the slurry C at 350 ℃ to obtain a ternary cathode composite material;
the first cladding is a three-dimensional nano-network layered structure and comprises a conductive polymer/graphene/carbon nano tube compound, and a hydrogen-containing lithium titanium oxide and FeF (FeF) dispersed on the surface of the compound in situ3(H2O)0.33The preparation method comprises the following steps:
(a) adding sodium dodecyl benzene sulfonate into a graphene oxide dispersion liquid to enable the mass ratio of graphene oxide to sodium dodecyl benzene sulfonate to be 1:1.5, fully dispersing the graphene oxide and the sodium dodecyl benzene sulfonate through ultrasonic waves under the power of 400W, then adding hydrazine hydrate to enable the mass ratio of the graphene oxide to the hydrazine hydrate to be 1:1.2, carrying out chemical reduction in a water bath at the temperature of 80 ℃, forming micelles among graphene layers through a surfactant in the process that the graphene oxide is reduced by the hydrazine hydrate, and centrifugally separating a product to remove the redundant sodium dodecyl benzene sulfonate serving as the surfactant to obtain the reduced graphene forming the micelles among the graphene layers.
(b) Dispersing the reduced graphene in ethanol, carrying out ultrasonic treatment for 5min under the power of 80W, then adding ethylene oxide, continuing ultrasonic treatment for 1.5h, adding ammonium persulfate with the mass 1.5 times that of polyoxyethylene, adding the hydroxylated single-walled carbon nanotube according to the proportion, wherein the phase structure of the single-walled carbon nanotube simultaneously contains Li1.81H0.19Ti2O5·H2O and TiO2With hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33Rapidly stirring at the speed of 1000 rpm in ice water bath at 0 ℃ for polymerization reaction for 25h, centrifugally separating the reaction product, and drying in vacuum at 65 ℃ to obtain the conductive polymer/graphene/carbon nanotube composite, the hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The coating material with the three-dimensional nano-network layered structure is prepared by an in-situ polymerization method.
Example 5
In the cathode material of this embodiment, the ternary cathode material is nickel cobalt lithium manganate, the molar ratio of nickel to cobalt to manganese is Ni to Co to Mn is 4 to 3, the mass percentage content of the first coating is 8%, the second coating is a carbonized product of polyvinyl alcohol, the usage amount of the polyvinyl alcohol is 5%,
in the first coating, a conductive polymer/graphene/carbon nanotube composite, a hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The mass ratio of (1) to (2) is 6.7:2.5: 0.8; the mass ratio of the conductive polymer to the graphene to the carbon nanotubes in the conductive polymer/graphene/carbon nanotube composite is 1.5:1.5: 3.5;
the preparation method of the cathode material comprises the following steps:
(1) dissolving polyvinyl alcohol (PVA) in a mixed solvent of water and ethanol (the volume ratio of the water to the ethanol is 1:1) to prepare a solution A;
(2) adding the first coating into the solution A obtained in the step (1), and uniformly stirring to obtain a solution B;
(3) adding a ternary cathode material into the solution B obtained in the step (2) to obtain slurry C, wherein the solid content of the slurry C is 65%;
(4) under the oxygen atmosphere, carrying out microwave treatment on the slurry C at the temperature of 400 ℃ to obtain a ternary cathode composite material;
the first cladding is a three-dimensional nano-network layered structure and comprises a conductive polymer/graphene/carbon nano tube compound, and a hydrogen-containing lithium titanium oxide and FeF (FeF) dispersed on the surface of the compound in situ3(H2O)0.33The preparation method comprises the following steps：
(a) Adding a proper amount of hexadecyl trimethyl ammonium bromide powder into a graphene oxide dispersion liquid to enable the mass ratio of graphene oxide to hexadecyl trimethyl ammonium bromide to be 1:0.3, fully dispersing the graphene oxide and the hexadecyl trimethyl ammonium bromide through ultrasonic waves under the power of 65W, then adding hydroxylated multi-walled carbon nanotubes and hydrazine hydrate to enable the mass ratio of the graphene oxide to the hydrazine hydrate to be 1:1.3, carrying out chemical reduction in a water bath at the temperature of 85 ℃, enabling a surfactant to form micelles among graphene layers in the process that the graphene oxide is reduced by the hydrazine hydrate, enabling the surfactant to form micelles on the surfaces of the carbon nanotubes, and centrifugally separating a product to remove the redundant surfactant hexadecyl trimethyl ammonium bromide to obtain the reduced graphene forming the micelles among the graphene layers and the carbon nanotubes with the micelles on the surfaces.
(b) Dispersing the reduced graphene in ethanol, carrying out ultrasonic treatment for 4min under the power of 350W, then adding pyrrole monomer, continuing ultrasonic treatment for 30min, adding ammonium persulfate with the mass being 0.5 time that of the pyrrole monomer, and adding hydrogen-containing lithium titanium oxide Li according to the proportion1.81H0.19Ti2O5·H2O and FeF3(H2O)0.33Rapidly stirring in ice water bath at 0 ℃ at the speed of 400 r/min for carrying out polymerization reaction for 24h, centrifugally separating the reaction product, and drying in vacuum at 50 ℃ to obtain the conductive polymer/graphene/carbon nano tube compound, the hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The coating material with the three-dimensional nano-network layered structure is prepared by an in-situ polymerization method.
Example 6
In the cathode material of this embodiment, the ternary cathode material is nickel cobalt lithium manganate, the molar ratio of nickel to cobalt to manganese is Ni to Co to Al is 8 to 1, the mass percentage content of the first coating is 5%, the second coating is a carbonized product of polyvinyl alcohol, the usage amount of the polyvinyl alcohol is 1%,
in the first coating, a conductive polymer/graphene/carbon nanotube composite, a hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The mass ratio of (1: 7) to (0.6); the mass ratio of the conductive polymer to the graphene to the carbon nanotubes in the conductive polymer/graphene/carbon nanotube composite is 1:2.5: 2.0;
(1) dissolving polyvinyl alcohol (PVA) in a mixed solvent of water and ethanol (the volume ratio of the water to the ethanol is 1:2) to prepare a solution A;
(2) adding the first coating into the solution A obtained in the step (1), and uniformly stirring to obtain a solution B;
(3) adding a ternary cathode material into the solution B obtained in the step (2) to obtain slurry C, wherein the solid content of the slurry C is 50%;
(4) under the air atmosphere, carrying out microwave treatment on the slurry C at the temperature of 450 ℃ to obtain a ternary cathode composite material;
the first cladding is a three-dimensional nano-network layered structure and comprises a conductive polymer/graphene/carbon nano tube compound, and a hydrogen-containing lithium titanium oxide and FeF (FeF) dispersed on the surface of the compound in situ3(H2O)0.33The preparation method comprises the following steps:
(a) adding a proper amount of hexadecyl trimethyl ammonium bromide powder into a graphene oxide dispersion liquid to enable the mass ratio of graphene oxide to hexadecyl trimethyl ammonium bromide to be 1:1.8, fully dispersing the graphene oxide and the hexadecyl trimethyl ammonium bromide through ultrasonic waves under the power of 250W, then adding hydrazine hydrate to enable the mass ratio of the graphene oxide to the hydrazine hydrate to be 1:2, carrying out chemical reduction in a water bath at the temperature of 95 ℃, forming micelles among graphene layers through a surfactant in the process that the graphene oxide is reduced by the hydrazine hydrate, and centrifugally separating a product to remove the redundant hexadecyl trimethyl ammonium bromide serving as the surfactant to obtain the reduced graphene with the micelles among the graphene layers.
(b) Dispersing the reduced graphene in ethanol, carrying out ultrasonic treatment for 4min under the power of 100W, then adding pyrrole monomer, continuing ultrasonic treatment for 1h, adding ammonium persulfate with the mass being 0.1 time of that of the pyrrole monomer, and adding a hydroxylated multi-walled carbon nanotube and a hydrogen-containing lithium titanium oxide Li according to the proportion1.81H0.19Ti2O5·H2O and FeF3(H2O)0.33At 0Rapidly stirring at 500 rpm in ice water bath for polymerization reaction for 27h, centrifuging the reaction product, and vacuum drying at 25 deg.C to obtain conductive polymer/graphene/carbon nanotube composite, hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The coating material with the three-dimensional nano-network layered structure is prepared by an in-situ polymerization method.
Comparative example 1
The comparative example is different from example 1 in that the first coating is not added in the preparation of the cathode material, and other conditions are identical to those of example 1.
Comparative example 2
The present comparative example is different from example 1 in that the carbon nanotube is not added in the preparation of the first clad and other conditions are completely the same as those of example 1.
Comparative example 3
The comparative example is different from example 1 in that polyvinyl alcohol is not added in the preparation of the positive electrode material, and other conditions are completely the same as those of example 1.
Comparative example 4
The comparative example is different from example 1 in that the microwave treatment temperature is 200 ℃ and other conditions are exactly the same as those of example 1.
Comparative example 5
This comparative example is different from example 1 in that the microwave treatment temperature was 650 deg.c, and other conditions were exactly the same as those of example 1.
And (3) performance testing:
adopting 2032 type button cell case, metal lithium foil (analytically pure) as counter electrode, and 1M LiPF6The solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio is 1:1) is used as electrolyte, and the battery diaphragm is a microporous polypropylene film (Celgard-2320). Stacking the positive diaphragm prepared by each application example in the order of 'stainless steel sheet, negative lithium sheet, electrolyte, diaphragm, electrolyte, positive diaphragm, stainless steel sheet and spring sheet', placing the stacked positive diaphragm, the stainless steel sheet and the spring sheet into a battery shell for sealing to prepare a button type lithium ion half battery, and performing electrochemistry on an Arbin machine in the United statesThe voltage test range of the battery is 2.8V-4.2V, and the button cell made of the positive electrode material in the above embodiment is tested for the first discharge specific capacity at 0.2C rate, the first coulombic efficiency and the capacity retention rate after 300 cycles (see table 1 for the result).
TABLE 1
Figure BDA0002347302040000181
Compared to example 1: comparative example 1 is not added with the first cladding material, can not provide more lithium ion transmission channels for the anode material, and has larger influence on the discharge specific capacity; comparative example 2 no carbon nanotube added in the first coating can not provide more electron conductivity to the positive electrode material, and has a certain influence on the discharge specific capacity and the cycle performance of the positive electrode material; comparative example 3 does not contain polyvinyl alcohol, so that the contact between the positive electrode material and the electrolyte can not be further effectively prevented, and the cycle performance and the specific discharge capacity are influenced; the microwave treatment temperature of the comparative example 4 is only 200 ℃, which can cause that the second cladding material polyvinyl alcohol can not effectively form a pyrolytic carbon material on the surface of the anode material, thereby influencing the specific capacity, the first coulombic efficiency and the cycle performance of the anode material; the microwave treatment temperature of comparative example 5 is 650 ℃, and too high temperature causes the second coating polyvinyl alcohol to be seriously decomposed to generate carbon dioxide, an effective coating layer cannot be formed on the surface of the anode material, the effect of preventing the contact between the electrolyte and the anode material cannot be achieved, the specific capacity is reduced, and the cycle performance is deteriorated.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (54)

1. The ternary cathode composite material is characterized by comprising a ternary cathode material core and a shell coated on the surface of the core, wherein the shell comprises a first coating and a second coating;
the first cladding is a three-dimensional nano-network layered structure and comprises a conductive polymer/graphene/carbon nano tube compound, and a hydrogen-containing lithium titanium oxide and FeF (FeF) dispersed on the surface of the compound in situ3(H2O)0.33The second coating is a carbonized product of polyvinyl alcohol;
the hydrogen-containing lithium titanium oxide compound is: the compound is composed of four elements of Li, H, Ti and O in any proportion, and the carbonization product of the polyvinyl alcohol is a carbon quantum dot.
2. The ternary positive electrode composite material according to claim 1, wherein the ternary positive electrode material core comprises any one or a combination of two of lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate.
3. The ternary positive electrode composite material according to claim 2, wherein the molar ratio of nickel, cobalt and manganese in the nickel cobalt lithium manganate is Ni: Co: Mn (4-9): (1-3): (2-3).
4. The ternary positive electrode composite according to claim 2, wherein the molar ratio of nickel, cobalt and aluminum in the nickel cobalt lithium aluminate is Ni: Co: Al (7-9):1: 1.
5. The ternary positive electrode composite according to claim 1, wherein the thickness of the outer shell is 1nm to 50 nm.
6. The ternary positive electrode composite according to claim 1, wherein the thickness of the outer shell is 2nm to 30 nm.
7. The ternary positive electrode composite material according to claim 1, wherein the mass percentage of the first coating material is 0.01% to 20% based on 100% by mass of the ternary positive electrode composite material.
8. The ternary positive electrode composite material according to claim 7, wherein the mass percentage of the first coating material is 0.1% to 15% based on 100% by mass of the ternary positive electrode composite material.
9. The ternary positive electrode composite material according to claim 1, wherein the mass percentage of the first coating material is 0.5% to 10% based on 100% by mass of the ternary positive electrode composite material.
10. The ternary positive electrode composite according to claim 1, wherein the first coating comprises a conductive polymer/graphene/carbon nanotube composite, a hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33The mass ratio of (6-9.4) to (0.5-3) to (0.1-1).
11. The ternary positive electrode composite material according to claim 1, wherein the mass ratio of the conductive polymer to the graphene to the carbon nanotubes in the conductive polymer/graphene/carbon nanotube composite is (0.1-2): (0.1-3): (0.5-5).
12. The ternary positive electrode composite according to claim 1, wherein the conductive polymer in the conductive polymer/graphene/carbon nanotube composite comprises at least one of polypyrrole, polyaniline, polythiophene or polyoxyethylene, or a copolymer formed from monomers of at least two conductive polymers.
13. The ternary positive electrode composite according to claim 1, wherein the graphene in the conductive polymer/graphene/carbon nanotube composite is formed by chemical reduction of graphene oxide.
14. The ternary positive electrode composite material of claim 1, wherein the carbon nanotubes in the conductive polymer/graphene/carbon nanotube composite are either single-walled carbon nanotubes or multi-walled carbon nanotubes or a combination of both.
15. The ternary positive electrode composite according to claim 1, wherein the carbon nanotubes in the conductive polymer/graphene/carbon nanotube composite are multiwalled carbon nanotubes.
16. The ternary positive electrode composite according to claim 1, wherein the hydrogen-containing lithium titanium oxide compound is: li is simultaneously present in any proportion in the phase structure4Ti5O12、TiO2And HxTiyOzThe compound of (1).
17. The ternary positive electrode composite according to claim 16, wherein the hydrogen-containing lithium titanium oxide is a compound having a phase structure in which Li is present simultaneously at an arbitrary ratio4Ti5O12And H2Ti3O7·(H2O·3TiO2) Wherein x is more than 0 and less than or equal to 2, y is more than 0 and less than or equal to 3, and z is more than 0 and less than or equal to 7.
18. The ternary positive electrode composite according to claim 1, wherein the hydrogen-containing lithium titanium oxide compound is: li1.81H0.19Ti2O5·aH2O, wherein a > 0.
19. The method of making a ternary positive electrode composite material according to claim 1, comprising the steps of:
(1) dissolving polyvinyl alcohol (PVA) in a solvent to prepare a solution A;
(2) adding the first coating into the solution A obtained in the step (1), and uniformly stirring to obtain a solution B;
(3) adding a ternary cathode material into the solution B obtained in the step (2) to obtain slurry C;
(4) under the atmosphere of air or oxygen, carrying out microwave treatment on the slurry C at the temperature of 300-500 ℃ to obtain a ternary cathode composite material;
the first cladding is a three-dimensional nano-network layered structure and comprises a conductive polymer/graphene/carbon nano tube compound, and a hydrogen-containing lithium titanium oxide and FeF (FeF) dispersed on the surface of the compound in situ3(H2O)0.33；
The hydrogen-containing lithium titanium oxide compound is: the compound is composed of four elements of Li, H, Ti and O in any proportion, and the carbonization product of the polyvinyl alcohol is a carbon quantum dot.
20. The method according to claim 19, wherein the polyvinyl alcohol is used in an amount of 0.1 to 5% based on 100% by mass of the ternary positive electrode composite material.
21. The method according to claim 19, wherein the polyvinyl alcohol is used in an amount of 0.5 to 2% based on 100% by mass of the ternary positive electrode composite material.
22. The method of claim 19, wherein the solvent of step (1) comprises water and/or ethanol.
23. The method of claim 19, wherein the first coating of step (2) is formed from a conductive polymer/graphene/carbon nanotube composite, a hydrogen-containing lithium titanium oxide, and FeF3(H2O)0.33A composite material prepared by in situ polymerization.
24. The method of claim 19, wherein the first coating of step (2) is prepared by:
(a) mixing graphene oxide with a surfactant, performing ultrasonic dispersion, mixing with a reducing agent, and performing chemical reduction to obtain reduced graphene forming micelles between graphene layers;
(b) dispersing the reduced graphene in the step (a) in a solvent, carrying out ultrasonic treatment, adding a conductive polymer monomer, continuing ultrasonic treatment, and adding an initiator, a carbon nano tube, a hydrogen-containing lithium titanium oxide and FeF3(H2O)0.33Carrying out polymerization reaction to obtain the coating material,
alternatively, the first coating in the step (2) is prepared by the following method:
firstly, mixing graphene oxide with a surfactant, performing ultrasonic dispersion, then mixing the graphene oxide with carbon nanotubes and a reducing agent, and performing chemical reduction to obtain a mixture of reduced graphene with micelles formed between graphene layers and carbon nanotubes with micelles formed on the surfaces;
dispersing the mixture obtained in the step one in a solvent, performing ultrasonic treatment, adding a conductive polymer monomer, continuing the ultrasonic treatment, and adding an initiator, a hydrogen-containing lithium titanium oxide compound and FeF3(H2O)0.33And carrying out polymerization reaction at 40 ℃ to obtain the coating material.
25. The method according to claim 24, wherein the surfactants of step (a) and step (r) independently comprise any one or a mixture of at least two of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, sodium dodecylsulfate or sodium dodecylbenzenesulfonate.
26. The method as claimed in claim 24, wherein the mass ratio of the graphene oxide to the reducing agent in the steps (a) and (c) is 1 (1-2).
27. The method as claimed in claim 26, wherein the mass ratio of the graphene oxide to the reducing agent in the steps (a) and (c) is 1 (1-1.5).
28. The process of claim 24, wherein the chemical reduction of step (a) and step (r) is carried out in a water bath at a temperature of 75 ℃ to 95 ℃.
29. The method of claim 24, wherein the ultrasonic power of steps (a) and (c) is 50W to 600W.
30. The method as claimed in claim 24, wherein in step (a) and step (r), the mass ratio of graphene oxide to surfactant is independently 1 (0.1-2).
31. The method as claimed in claim 30, wherein in step (a) and step (r), the mass ratio of graphene oxide to surfactant is independently 1 (0.3-1.5).
32. The method of claim 24, wherein the reducing agents of step (a) and step (r) independently comprise either sodium borohydride or hydrazine hydrate or a combination of both.
33. The method of claim 32, wherein the reducing agent in steps (a) and (c) is hydrazine hydrate.
34. The method of claim 24, wherein the solvent of steps (b) and (c) comprises any one or a mixture of at least two of chloroform solution of ferric chloride, ethanol, deionized water, or inorganic protic acid.
35. The method of claim 24, wherein the power of the ultrasound in steps (b) and (c) is 80W to 500W.
36. The method of claim 24, wherein the time for continuing the ultrasound in step (b) and step (ii) is independently 30min-2 h.
37. The method of claim 24 wherein in step (b) and step (c), the initiator is ammonium persulfate.
38. The process of claim 24 wherein in steps (b) and (c), the amount of initiator added is independently from 0.1 to 2 times the mass of polymer monomer added.
39. The process of claim 38 wherein in steps (b) and (c), the amount of initiator added is independently from 0.5 to 1.5 times the mass of polymer monomer added.
40. The process of claim 24, wherein steps (b) and (c) are carried out in an ice-water bath.
41. The process of claim 24 wherein step (b) and step (ii) are carried out with agitation at a rate of from 500 to 3000 r/min.
42. The process of claim 24, wherein the polymerization reaction time of step (b) and step (c) is independently from 12h to 30 h.
43. The method of claim 24, wherein the carbon nanotubes of step (b) and step (r) are independently single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
44. The method of claim 24, wherein the carbon nanotubes of steps (b) and (c) are hydroxylated carbon nanotubes.
45. The method of claim 44, wherein the carbon nanotubes of step (b) and step (r) are hydroxylated multi-wall carbon nanotubes.
46. The method of claim 24, further comprising the step of separating and removing excess surfactant after said chemical reduction of step (a) and step (r).
47. The method of claim 24 further comprising the steps of separating and drying after steps (b) and (c) said polymerization reaction.
48. The method of claim 47, wherein the drying is vacuum drying at 50 ℃ to 70 ℃.
49. The method of claim 19, wherein the ternary positive electrode material of step (3) comprises any one of or a combination of nickel cobalt lithium manganate or nickel cobalt lithium aluminate.
50. The method of claim 24, wherein the slurry C in step (3) has a solid content of 20-70%.
51. The method as claimed in claim 50, wherein the slurry C in the step (3) has a solid content of 30-60%.
52. The method of claim 19, wherein the temperature of the microwave treatment in step (3) is 350 ℃ to 450 ℃.
53. The method according to claim 19, characterized in that it comprises the steps of:
(1) dissolving polyvinyl alcohol (PVA) in water and/or ethanol to prepare a solution A;
(2) adding the first coating into the solution A obtained in the step (1), and uniformly stirring to obtain a solution B;
(3) adding a ternary cathode material into the solution B obtained in the step (2) to obtain slurry C, wherein the solid content of the slurry C is 20-70%;
(4) under the atmosphere of air or oxygen, carrying out microwave treatment on the slurry C at the temperature of 300-500 ℃ to obtain a ternary cathode composite material;
the first cladding is a three-dimensional nano-network layered structure and comprises a conductive polymer/graphene/carbon nano tube compound, and a hydrogen-containing lithium titanium oxide and FeF (FeF) dispersed on the surface of the compound in situ3(H2O)0.33；
The usage amount of the polyvinyl alcohol is 0.1-5% based on the total mass of the prepared ternary cathode composite material as 100%.
54. Use of the ternary positive electrode composite according to any of claims 1 to 18, characterized in that said positive electrode material is used in lithium ion batteries.
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CN111628176B (en) * 2020-06-17 2022-01-28 苏州盟维动力科技有限公司 Multi-component three-dimensional conductive carbon network, self-supporting composite electrode, and preparation methods and applications thereof
CN114068890B (en) * 2020-08-07 2023-12-08 华为技术有限公司 Composite metal negative electrode, preparation method thereof, secondary battery and terminal
CN111785960B (en) * 2020-09-03 2020-11-20 中南大学 Vanadium pentoxide/rGO coated nickel cobalt lithium manganate positive electrode material and preparation method thereof
CN112599779A (en) * 2020-12-15 2021-04-02 上海华谊（集团）公司 Double-layer coated lithium ion battery anode material and preparation method thereof
CN114566636B (en) * 2021-12-29 2023-11-17 中国科学院过程工程研究所 Lithium-rich manganese-based positive electrode material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105958020A (en) * 2016-05-26 2016-09-21 湘潭大学 Method for preparing nanometer FeF<3>.0.33H<2>O by alcohol-thermal method
CN107845786A (en) * 2017-09-27 2018-03-27 中国科学院过程工程研究所 A kind of hud typed positive electrode, its preparation method and the purposes in lithium ion battery of composite cladding
CN109860534A (en) * 2018-12-18 2019-06-07 中科廊坊过程工程研究院 A kind of tertiary cathode material and preparation method thereof of carbon quantum dot modification
CN110272067A (en) * 2019-06-25 2019-09-24 浙江大学 A kind of preparation method being hydrated laminar nano lithium titanate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105958020A (en) * 2016-05-26 2016-09-21 湘潭大学 Method for preparing nanometer FeF<3>.0.33H<2>O by alcohol-thermal method
CN107845786A (en) * 2017-09-27 2018-03-27 中国科学院过程工程研究所 A kind of hud typed positive electrode, its preparation method and the purposes in lithium ion battery of composite cladding
CN109860534A (en) * 2018-12-18 2019-06-07 中科廊坊过程工程研究院 A kind of tertiary cathode material and preparation method thereof of carbon quantum dot modification
CN110272067A (en) * 2019-06-25 2019-09-24 浙江大学 A kind of preparation method being hydrated laminar nano lithium titanate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Improving cycling performance and rate capability of Ni-rich LiNi0.8Co0.1Mn0.1O2cathode materials by Li4Ti5O12 coating;Ya-Di Xu等;《Electrochimica Acta》;20180209;第268卷;第358-365页 *

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