CN111509198A - Core-shell structure composite material, preparation method thereof and application thereof in lithium ion battery - Google Patents
Core-shell structure composite material, preparation method thereof and application thereof in lithium ion battery Download PDFInfo
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- CN111509198A CN111509198A CN201910098550.4A CN201910098550A CN111509198A CN 111509198 A CN111509198 A CN 111509198A CN 201910098550 A CN201910098550 A CN 201910098550A CN 111509198 A CN111509198 A CN 111509198A
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- lithium titanate
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- 239000002131 composite material Substances 0.000 title claims abstract description 97
- 239000011258 core-shell material Substances 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 10
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 72
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 61
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Materials Engineering (AREA)
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- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses a core-shell structure composite material, a preparation method thereof and application in a lithium ion battery. In the core-shell structure composite material, the core mainly comprises a hard carbon material, the shell is a composite coating layer formed by compounding nano lithium titanate particles and a carbonized binder, and the nano lithium titanate particles are fixed and dispersed on the surface of the core by the carbonized binder. The method comprises the following steps: 1) preparing a hard carbon material as a core; 2) the method comprises the following steps of (1) adopting nano lithium titanate particles, a binder and an inner core as raw materials, and fixing the nano lithium titanate on the surface of the inner core through the curing action of the binder to obtain a product consisting of the inner core and a composite coating layer precursor coated on the surface of the inner core; 3) pre-sintering, and then sintering to obtain the core-shell structure composite material. The core-shell structure composite material has the advantages of high compaction, high capacity, high first charge-discharge efficiency and good cycle stability, and has wide application prospect in the field of lithium ion batteries.
Description
Technical Field
The invention relates to the field of lithium ion battery cathode materials, in particular to a core-shell structure composite material, a preparation method thereof and application thereof in a lithium ion battery. The invention relates to a multi-element composite hard carbon negative electrode material, a preparation method thereof and a lithium ion battery containing the same.
Background
Lithium ion batteries have been widely used in portable electronic products and electric vehicles because of their advantages of high operating voltage, long cycle life, no memory effect, low self-discharge, and environmental friendliness. Amorphous carbon materials can be classified into soft carbon and hard carbon according to the ease of graphitization. The soft carbon is carbon which can be graphitized at 2500 ℃ or higher, and the hard carbon is carbon which is difficult to be graphitized at 2500 ℃ or higher. The structural units of hard carbon (graphitic crystallites) are arranged in a cross-linked manner, while the structural units of soft carbon are arranged in a more parallel manner; the interlayer spacing d002 of hard carbon is greater than that of soft carbon. Therefore, hard carbon has rate and cycle performance superior to those of soft carbon. In addition, the hard carbon material also has the characteristics of large capacity, low manufacturing cost, good safety performance and the like. In 1991, Sony corporation first prepared a hard carbon material using polyfurfuryl alcohol (PFA) as a precursor, and used as a negative electrode material of a lithium ion battery, thereby attracting much attention. According to the classification of precursors, hard carbons can be classified into plant-based hard carbons and high-molecular polymer pyrolytic carbons. The former precursor comprises starch, oak, walnut shell, almond shell, maple, lignin, etc.; the latter precursors include resins and other polymers including phenolic resins (epoxy resins), epoxy resins (epoxy resins), melamine resins, polyfurfuryl alcohol (PFA), polyphenylenes (PP), Polyacrylonitriles (PAN), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polyphenylenesulfides, polynaphthalenes, cellulose, etc., and further carbon black (acetylene black AB), Benzene Carbon (BC). As for the lithium storage mechanism, the lithium storage mechanism of graphite is that lithium is inserted into graphite to form a graphite insertion compound, and the lithium storage mechanism of hard carbon is various, including a lithium molecular mechanism, a multi-layer lithium mechanism, a lattice mechanism, an elastic sphere-elastic network model, a layer-edge-surface mechanism, a nano-scale graphite lithium storage mechanism, a carbon-lithium-hydrogen mechanism, a single-layer ink sheet molecular mechanism, and a microporous lithium storage mechanism. As such, hard carbon tends to exhibit characteristics higher than the theoretical capacity of graphite. With the rise of electric vehicles and the requirement of the electric vehicles on the endurance capacity of power batteries, the traditional graphite materials cannot meet the requirement more and more. Hard carbon materials are one of the ideal negative electrode materials for power batteries because of their excellent capacity, rate, and cycle characteristics.
However, the hard carbon material is limited in practical application due to its low first irreversible capacity and low specific volumetric capacity, and therefore, it is necessary to develop a hard carbon material with high capacity, high first efficiency and high compaction. At present, two methods of improving the volume specific capacity and the first charge-discharge efficiency of the hard carbon material are doping modification and cladding modification.
CN 107732245a discloses a preparation method of a hard carbon/graphene composite negative electrode material for a lithium battery, which is to mix an organic carbon source after stabilization treatment with lamellar graphene in an organic solvent, perform ultrasonic treatment and then perform a heating reaction to obtain a hard carbon/graphene composite precursor; then mixing the precursor with nano spherical metal powder, carrying out high-temperature thermal decomposition under the protection of inert gas to form spherical hard carbon to coat the surface of the nano spherical metal powder, and sandwiching the spherical hard carbon between layered graphene to obtain a hard carbon/graphene composite negative electrode material; but the prepared hard carbon material has lower compaction density, so that the specific volume capacity of the material is greatly reduced. In addition, the problem of low first coulombic efficiency of hard carbon materials is not solved.
Therefore, the research and development of the multi-element composite hard carbon negative electrode material with high compaction, high capacity, high first charge-discharge efficiency and good cycle stability is a technical problem in the field of lithium ion batteries.
Disclosure of Invention
Aiming at the defects of the prior art, one of the purposes of the invention is to provide a core-shell structure composite material, a preparation method thereof and application thereof in a lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a core-shell structure composite material, which is a multi-element composite hard carbon material with a core-shell structure, wherein the core of the core-shell structure composite material mainly comprises a hard carbon material, the shell is a composite coating layer formed by compounding nano lithium titanate particles and a carbonized binder, and the nano lithium titanate particles are fixed and dispersed on the surface of the core by the carbonized binder.
In the composite material, the core is mainly hard carbon, the shell is a composite coating layer (which is a nano composite) formed by compounding nano lithium titanate particles and a carbonized binder, and the nano lithium titanate in the shell layer is firmly adhered to the surface of the hard carbon of the core to form the stable core-shell structure composite material with layered inner and outer layers and uniformly distributed nano lithium titanate particles.
As a preferred technical scheme of the core-shell structure composite material, the hard carbon material is prepared by using a plant raw material as a carbon source, and the shape of the hard carbon material is any 1 or a combination of at least 2 of a sheet shape, a block shape, a sphere shape or a spherical shape.
According to the invention, plant raw materials are selected as a carbon source to prepare the hard carbon material, and the hard carbon material is matched with a binder and nano lithium titanate to prepare the core-shell structure composite material.
Preferably, the plant-based raw material includes, but is not limited to, any 1 or a combination of at least 2 of rice hulls, corn cobs, fruit shells, or herbaceous plant stems.
In a preferred embodiment of the core-shell structure composite material of the present invention, the median particle diameter of the core is 0.5 μm to 30 μm, such as 0.5 μm, 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm, or 30 μm, preferably 3 μm to 25 μm, and more preferably 5 μm to 18 μm.
Preferably, the nano lithium titanate particles are in the shape of any 1 or a combination of at least 2 of a sheet, a block, a sphere or a sphere.
Preferably, the nano lithium titanate particles have a median particle size of 25nm to 1000nm, such as 25nm, 35nm, 50nm, 60nm, 70nm, 80nm, 100nm, 120nm, 135nm, 150nm, 200nm, 220nm, 240nm, 260nm, 280nm, 320nm, 360nm, 400nm, 450nm, 500nm, 525nm, 570nm, 600nm, 650nm, 700nm, 750nm, 800nm, 900nm, 1000nm, etc., preferably 25nm to 600nm, more preferably 25nm to 300 nm.
As a preferred technical scheme of the core-shell structure composite material, the binder comprises any 1 or a combination of at least two of asphalt, epoxy resin, phenolic resin, furfural resin, urea-formaldehyde resin or acrylic resin, but is not limited to the above listed binders, and other binders with the characteristics that ① can be dissolved in a solvent, ② can be cured under certain conditions, and a composite coating layer formed by ③ and nano lithium titanate particles has electrochemical activity on lithium can also be used in the invention.
More preferably, the binder is asphalt, and further preferably any 1 or a combination of at least 2 of medium-temperature coal asphalt, medium-temperature petroleum asphalt, high-temperature coal asphalt, high-temperature petroleum asphalt, or emulsified petroleum asphalt.
More preferably, the nanometer lithium titanate particles and high-temperature asphalt (such as high-temperature coal asphalt and/or high-temperature petroleum asphalt) are matched for use, so that the structure can be optimally regulated and controlled, and a composite coating layer with electrochemical activity on lithium can be formed.
Preferably, the carbonized binder has a carbon content of 40% or more, such as 40%, 50%, 60%, 70%, 80%, 85%, or the like.
As a preferred embodiment of the core-shell structure composite material of the present invention, the core-shell structure composite material contains 1 wt% to 40 wt% of nano lithium titanate particles, for example, 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 17 wt%, 22 wt%, 26 wt%, 30 wt%, 35 wt%, 37.5 wt%, or 40 wt%, based on 100 wt% of the total mass of the core-shell structure composite material; 30 wt% to 80 wt%, such as 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 70 wt%, or 80 wt%, etc., of a hard carbon material; the carbonized binder is 5 to 40 wt%, for example, 5, 10, 15, 20, 25, 27.5, 30, 35, 40 wt%, etc.
More preferably, the core-shell structure composite material contains 1 wt% to 25 wt% of nano lithium titanate particles, such as 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 17 wt%, 22 wt%, 25 wt%, etc.; hard carbon material 55 wt% to 80 wt%, such as 55 wt%, 60 wt%, 70 wt%, or 80 wt%, etc.; the carbonized binder is 5 wt% to 20 wt%, for example, 5 wt%, 10 wt%, 15 wt%, 20 wt%, etc. The more preferable proportion is more beneficial to constructing the core-shell structure of the composite material and obtaining excellent material performance.
The median particle diameter of the core-shell structure composite material is 0.5 to 40 μm, for example, 0.5, 1, 2, 5, 10, 12, 16, 20, 23, 25, 27, 30, 35 or 40 μm, preferably 2 to 30 μm, and more preferably 5 to 25 μm.
In a second aspect, the present invention provides a method for preparing a core-shell structure composite material according to the first aspect, the method comprising the steps of:
(1) preparing a hard carbon material as a core;
(2) the method comprises the following steps of (1) adopting nano lithium titanate particles, a binder and an inner core as raw materials, and fixing the nano lithium titanate on the surface of the inner core through the curing action of the binder to obtain a product consisting of the inner core and a composite coating layer precursor coated on the surface of the inner core;
(3) pre-sintering, and then sintering to obtain the core-shell structure composite material.
In the method, the pre-sintering is an essential step, the function is to cure the binder, the fixation of nano lithium titanate particles uniformly dispersed on the surface of the hard carbon material is realized in the curing process of the binder, and finally, the fixation is further strengthened by carbonizing the binder through sintering treatment, so that the composite material which takes the hard carbon as a core and lithium titanate as a shell and is tightly fixed by the carbonized binder is successfully prepared, and the composite material is a cathode material for the lithium ion battery with excellent performance.
As a preferred technical scheme of the method, the step (1) specifically comprises the following steps:
crushing, carbonizing and crushing the plant raw materials to obtain the hard carbon material.
Preferably, it is crushed to 0.5mm-5mm, such as 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, or 5mm, etc.
Preferably, the carbonization temperature is 500-650 ℃, such as 500 ℃, 520 ℃, 550 ℃, 580 ℃, 600 ℃, 620 ℃ or 650 ℃, and the like, and the time is 0.5h-3h, such as 0.5h, 1h, 1.5h, 2h, 2.5h or 3h, and the like.
Preferably, the pulverization is a jet pulverization, and further a pulverization is carried out to a median particle diameter of 0.5 to 30 μm, such as 0.5 to 1 μm, 5 to 10 μm, 15 to 20, 25 or 30 μm, preferably 3 to 25 μm, and more preferably 5 to 18 μm.
As a preferred embodiment of the method of the present invention, the method of step (2) is any 1 or 2 combination of liquid phase coating method or solid phase coating method.
Preferably, the liquid phase coating method is any one of the first mode or the second mode:
the first mode comprises the following steps: dispersing nano lithium titanate particles and a binder in an organic solvent to obtain slurry, then placing the core obtained in the step (1) in the slurry, and reacting in a rotary evaporator to obtain a product consisting of the core and a composite coating layer precursor coated on the surface of the core;
the second mode includes: and (2) directly dispersing the nano lithium titanate particles, the binder and the core obtained in the step (1) in an organic solvent, and reacting in a rotary evaporator to obtain a product consisting of the core and a composite coating layer precursor coated on the surface of the core.
Preferably, in the liquid phase coating method, the dispersion is performed by: adding the nano lithium titanate particles and the binder into an organic solvent, placing the organic solvent in a rotary evaporator, and rotating until the slurry is completely and uniformly dispersed to obtain slurry.
Preferably, in the liquid phase coating method, the first substance is dispersed in an organic solvent, and a dispersant is further included.
Preferably, in the liquid phase coating method, the substance dispersed in the organic solvent further includes a dispersant.
Preferably, the dispersant in mode one and mode two is independently any 1 or a combination of at least 2 of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexylphosphoric acid, sodium lauryl sulfate, methylpentanol, cellulose derivatives, polyacrylamide, guar gum, polyethylene glycol esters of fatty acids, cetyltrimethylammonium bromide, polyethylene glycol p-isooctylphenyl ether, polyacrylic acid, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate, p-ethylbenzoic acid, or polyetherimide.
Preferably, in the first and second modes, the mass ratio of the dispersant added is 0.1% to 3% of the total weight of the core and the lithium titanate, such as 0.1%, 0.2%, 0.5%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8% or 3%, and the like, preferably 0.2% to 1.5%;
preferably, the organic solvent in the first and second modes is independently any 1 or a combination of at least 2 of alcohol, ketone or ether. The organic solvent of the present invention needs to be capable of dissolving the binder used in combination therewith, and the organic solvent may be selected according to the kind of the binder in the art.
Preferably, the first and second modes further comprise a step of cooling after the reaction is completed.
Firstly, adding nano lithium titanate particles and a binder into an organic solvent for dispersion, so that the lithium titanate particles can be dispersed more uniformly; and in the second mode, the nano lithium titanate particles, the binder and the core are simultaneously added into the organic solvent, so that the dispersing effect of the lithium titanate is poor, and the industrialization is facilitated.
Preferably, the solid phase coating method comprises: and (2) placing the nano lithium titanate particles, the binder and the core obtained in the step (1) into a fusion machine for fusion to obtain a product consisting of the core and a composite coating layer precursor coated on the surface of the core.
Preferably, in the solid-phase coating method, the rotation speed of the fusion machine is 500r/min to 3000r/min, such as 500r/min, 650r/min, 800r/min, 1000r/min, 1200r/min, 1500r/min, 1750r/min, 2000r/min, 2200r/min, 2400r/min, 2600r/min, 2850r/min or 3000r/min, etc., and the width of the cutter gap is 0.01cm to 0.5cm, such as 0.01cm, 0.04cm, 0.08cm, 0.1cm, 0.15cm, 0.2cm, 0.25cm, 0.3cm, 0.35cm, 0.4cm or 0.5cm, etc.
Preferably, in the solid-phase coating method, the fusion time is not less than 0.5 h.
As a preferred embodiment of the method of the present invention, the pre-sintering in step (3) is performed under the protection of a protective gas, which includes but is not limited to any 1 or at least 2 combinations of nitrogen, helium, neon, argon, or xenon.
Preferably, the temperature of the pre-sintering in the step (3) is 200 ℃ to 500 ℃, such as 200 ℃, 270 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃ or 500 ℃, etc.
Preferably, in step (3), the temperature raising rate for raising the temperature to the pre-sintering temperature is 0.5 ℃/min to 20 ℃/min, such as 0.5 ℃/min, 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 7 ℃/min, 10 ℃/min, 13 ℃/min, 15 ℃/min, 18 ℃/min or 20 ℃/min, and the like, preferably 2 ℃/min to 5 ℃/min.
Preferably, the pre-sintering time in step (3) is 0.5h to 10h, such as 0.5h, 1h, 3h, 5h, 7h, 8h or 10h, etc., preferably 0.5h to 5 h.
Preferably, the sintering of step (3) is performed under the protection of a protective gas, wherein the protective gas comprises any 1 or at least 2 of nitrogen, helium, neon, argon or xenon.
Preferably, the sintering temperature in step (3) is 600 ℃ to 1200 ℃, such as 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, and the like.
Preferably, in step (3), the heating rate of heating to the sintering temperature is 0.5 ℃/min to 20 ℃/min, such as 1 ℃/min, 2 ℃/min, 3 ℃/min, 5 ℃/min, 7 ℃/min, 10 ℃/min, 12 ℃/min, 15 ℃/min, 18 ℃/min or 20 ℃/min, and the like, preferably 2 ℃/min to 5 ℃/min.
Preferably, the sintering time in step (3) is 0.5h to 10h, such as 0.5h, 2h, 3h, 6h, 7h, 8h, 9h or 10h, etc., preferably 0.5h to 5 h.
Preferably, the reactor for performing the pre-sintering and sintering of step (3) is independently any one of a vacuum furnace, a box furnace, a rotary furnace, a roller kiln, a pusher kiln and a tube furnace.
As a preferred technical scheme of the method, the inner core obtained in the step (1) is sieved before being used as a raw material to carry out the step (2) so as to remove large particles.
Preferably, the method further comprises the step of performing demagnetization, purification and screening treatment after the step (3) of pre-sintering and before the sintering treatment, wherein the screening treatment removes large particles.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) preparing a hard carbon material as an inner core, which specifically comprises the following steps:
crushing, carbonizing and carrying out jet milling on plant raw materials to obtain a hard carbon material;
sieving the hard carbon material to remove large particles;
(2) adding nano lithium titanate particles, a binder and a dispersant into an organic solvent, placing the organic solvent in a rotary evaporator, rotating the organic solvent until slurry is completely and uniformly dispersed to obtain slurry, then placing the core obtained by sieving in the step (1) in the slurry, and reacting the slurry in the rotary evaporator for 0.5 to 10 hours to fix the nano lithium titanate on the surface of the core under the curing action of the binder, thereby obtaining a product consisting of the core and a composite coating layer precursor coated on the surface of the core;
(3) presintering for 0.5 h-10 h at 200 ℃ -500 ℃ under the protection of protective gas, then demagnetizing, purifying and screening, and sintering for 0.5 h-10 h at 600 ℃ -1200 ℃ under the protection of protective gas to obtain the core-shell structure composite material.
As another preferred embodiment of the method of the present invention, the method comprises the steps of:
(1) preparing a hard carbon material as an inner core, which specifically comprises the following steps:
crushing, carbonizing and carrying out jet milling on plant raw materials to obtain a hard carbon material;
sieving the hard carbon material to remove large particles;
(2) placing the nano lithium titanate particles, the binder and the core obtained in the step (1) into a fusion machine for fusion, wherein the rotation speed of the fusion machine is 500-3000 r/min, the width of a cutter gap is 0.01-0.5 cm, and the fusion time is not less than 0.5h, so as to obtain a product consisting of the core and a composite coating layer precursor coated on the surface of the core;
(3) presintering for 0.5 h-10 h at 200 ℃ -500 ℃ under the protection of protective gas, then demagnetizing, purifying and screening, and sintering for 0.5 h-10 h at 600 ℃ -1200 ℃ under the protection of protective gas to obtain the core-shell structure composite material.
In a third aspect, the present invention provides a lithium ion battery, which includes the core-shell structure composite material according to the first aspect as a negative electrode active material.
The type of the lithium ion battery is not particularly limited, and the lithium ion battery can be a conventional aluminum shell, a steel shell or a soft package lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, an in-situ coating method is adopted, the binder and the nano lithium titanate particles are matched for use, and the nano lithium titanate particles are fixed in situ in the binder curing and carbonizing processes, so that the nano lithium titanate particles can be uniformly and compactly coated on the surface of the hard carbon material core, the uniformity of the material structure is ensured, and the structural stability of the core-shell material is improved.
Moreover, the invention utilizes the instruments such as a rotary evaporator, a vacuum furnace, a box furnace, a rotary furnace, a roller kiln, a pushed slab kiln or a tube furnace and the like, and has the characteristics of simple preparation process, low raw material cost and convenient industrial production.
(2) The composite material has a special core-shell structure, the structure is stable, the main core is mainly made of hard carbon materials, the high-capacity advantage of the material is guaranteed, the shell is a composite coating layer formed by uniformly dispersed nano lithium titanate particles and carbonized binder, and the carbonized binder firmly adheres to the surface of the core. The composite material has unique structure and component matching, so that the composite material has excellent rate performance, first effect, high pole piece compaction and the like, and has obvious advantages compared with other current coating materials.
The powder compaction density of the composite material is more than or equal to 0.95g/cc, the initial capacity of the composite material is more than or equal to 350mAh, and the first effect is more than or equal to 87 percent when the composite material is applied to a lithium ion battery cathode material.
Drawings
Fig. 1a to fig. 1d are electron microscope images of the novel multi-component composite hard carbon negative electrode material in example 1 of the present invention;
fig. 2 a-2 d are EDS scanning pictures of the novel multi-component composite hard carbon negative electrode material in example 1 of the present invention;
fig. 3 is a first charge-discharge comparison graph obtained by testing batteries respectively made of the novel multi-element composite hard carbon negative electrode materials in the embodiment 1 and the embodiment 2 of the invention and the product in the comparative example 1.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
(1) The method for preparing the hard carbon material with the grain diameter of 5-18 mu m by taking plant raw materials as a carbon source specifically comprises the following steps: crushing, carbonizing and jet milling;
(2) dispersing the plant hard carbon material, lithium titanate nano particles with the particle size of 30-250nm and high-temperature petroleum asphalt into propanol according to the mass ratio of 80:5:15, performing rotary evaporation drying at 30 ℃, and adjusting the rotating speed to 30.0r/min to obtain a coating material precursor;
(3) then placing the precursor in a box-type furnace, introducing argon, heating to 500 ℃ at the heating rate of 2.0 ℃/min, preserving the heat for 2.0h, and naturally cooling to room temperature to obtain a third precursor; and crushing, screening and demagnetizing the third precursor to obtain a fourth precursor with the particle size of 5.0-45.0 microns, finally placing the fourth precursor in a box-type furnace, introducing argon, heating to 1100.0 ℃ at the heating rate of 2.0 ℃/min, preserving the temperature for 2.0h, and naturally cooling to room temperature to obtain the novel multi-element composite hard carbon negative electrode material, namely the core-shell structure composite material.
Fig. 1a to fig. 1d are electron microscope pictures of the novel multi-component composite hard carbon negative electrode material in this embodiment, and it can be seen from the pictures that the surface of the prepared material is uniformly and densely coated.
Fig. 2a to fig. 2d are EDS scanning pictures of the novel multi-component composite hard carbon negative electrode material in this embodiment, and it can be seen from the drawings that lithium titanate in the material is uniformly distributed.
Example 2
(1) The method for preparing the hard carbon material by taking plant raw materials as a carbon source specifically comprises the following steps: crushing, carbonizing and jet milling;
(2) placing the plant hard carbon material, lithium titanate nano particles with the particle size of 30-250nm and high-temperature petroleum asphalt in a fusion machine according to the mass ratio of 80:5:15, adjusting the rotating speed to 2000.0r/min, adjusting the width of a cutter gap to 0.5cm, and fusing for 0.5h to obtain a coating material precursor;
(3) then placing the precursor in a box-type furnace, introducing argon, heating to 500 ℃ at the heating rate of 2.0 ℃/min, preserving the heat for 2.0h, and naturally cooling to room temperature to obtain a third precursor; and crushing, screening and demagnetizing the third precursor to obtain a fourth precursor with the particle size of 5.0-45.0 microns, finally placing the fourth precursor in a box-type furnace, introducing argon, heating to 1100.0 ℃ at the heating rate of 2.0 ℃/min, preserving the temperature for 2.0h, and naturally cooling to room temperature to obtain the novel multi-element composite negative hard carbon negative electrode material, namely the core-shell structure composite material.
Fig. 3 is a first charge-discharge curve diagram obtained by testing batteries respectively made of the novel multi-component composite hard carbon negative electrode materials in examples 1 and 2 of the invention and the product of comparative example 1, and it can be seen that the novel multi-component composite hard carbon negative electrode material of the invention has high first charge-discharge efficiency.
Example 3
(1) Preparing a hard carbon material as an inner core;
(2) dispersing lithium titanate nano particles with the particle size of 30-250nm and high-temperature coal pitch into propanol according to the mass ratio of 5:15, performing rotary evaporation drying, adjusting the rotating speed to 60.0r/min, rotating until the slurry is completely and uniformly dispersed to obtain slurry, then placing 80 parts of the hard carbon material core into the slurry, and performing reaction in a rotary evaporator at 55 ℃ for 4 hours to obtain a coating material precursor;
(3) then placing the precursor in a box type furnace, introducing nitrogen, heating to 450.0 ℃ at the heating rate of 3.0 ℃/min, preserving the heat for 6.0h, and naturally cooling to room temperature to obtain a third precursor; and crushing, screening and demagnetizing the third precursor to obtain a fourth precursor with the particle size of 5.0-45.0 microns, finally placing the fourth precursor in a box-type furnace, introducing argon, heating to 900.0 ℃ at the heating rate of 5.0 ℃/min, preserving heat for 3.5 hours, and naturally cooling to room temperature to obtain the novel multi-element composite hard carbon negative electrode material, namely the core-shell structure composite material.
Example 4
(1) Preparing hard carbon material (the grain diameter is between 5 and 18.0 mu m) as an inner core;
(2) dispersing lithium titanate nanoparticles with the particle size of 25-100nm, phenolic resin and sodium tripolyphosphate into acetone according to the weight ratio of 5:15:0.4, adjusting the rotating speed to 85.0r/min, rotating until the slurry is completely and uniformly dispersed to obtain slurry, then placing the hard carbon material core into the slurry, and reacting for 2 hours at 70 ℃ in a rotary evaporator to obtain a coating material precursor;
(3) then placing the precursor in a box type furnace, introducing nitrogen, heating to 350.0 ℃ at the heating rate of 7.0 ℃/min, preserving the heat for 8.0h, and naturally cooling to room temperature to obtain a third precursor; and crushing, screening and demagnetizing the third precursor to obtain a fourth precursor with the particle size of 5.0-45.0 microns, finally placing the fourth precursor in a tube furnace, introducing nitrogen, heating to 1050.0 ℃ at the heating rate of 12.0 ℃/min, preserving heat for 6 hours, and naturally cooling to room temperature to obtain the novel multi-element composite hard carbon negative electrode material, namely the core-shell structure composite material.
Example 5
(1) Preparing a hard carbon material (5-18.0 μm) as an inner core;
(2) placing the plant hard carbon material precursor, lithium titanate nano-particles with the particle size of 50-100nm and furfural resin in a fusion machine according to the mass ratio of 80:5:15, adjusting the rotating speed to 1000.0r/min, adjusting the width of a cutter gap to 0.2cm, and fusing for 4 hours to obtain a coating material precursor;
(3) then placing the precursor in a box-type furnace, introducing argon, heating to 400.0 ℃ at the heating rate of 8.0 ℃/min, preserving the heat for 8.0h, and naturally cooling to room temperature to obtain a third precursor; and crushing, screening and demagnetizing the third precursor to obtain a fourth precursor with the particle size of 5.0-45.0 microns, finally placing the fourth precursor in a box-type furnace, introducing argon, heating to 1150.0 ℃ at the heating rate of 15.0 ℃/min, preserving the temperature for 5.5 hours, and naturally cooling to room temperature to obtain the novel multi-element composite negative hard carbon negative electrode material, namely the core-shell structure composite material.
Comparative example 1
A composite material was prepared in substantially the same manner as in example 2, except that: and (3) directly compounding the hard carbon second precursor with asphalt without adding lithium titanate nano particles, placing the compound in a fusion machine, fusing to obtain a coating material precursor, and then performing subsequent carbonization to obtain a composite material product.
Comparative example 2
The preparation process was carried out in substantially the same manner as in example 1 except that: the preparation method comprises the steps of firstly carrying out carbon coating on lithium titanate nano particles by using high-temperature petroleum asphalt to obtain coated particles, and then dispersing the coated particles on the surface of a hard carbon core by adopting a traditional method to obtain a composite material product.
The composite materials obtained in examples 1-5 and comparative examples 1-2 were tested for various properties by the following methods:
the representation of the micro-morphology adopts a Hitachi S-4800 scanning electron microscope;
the characterization of the material element distribution adopts a Hitachi S-4800 scanning electron microscope;
the electrochemical performance is tested by adopting the following method that the composite materials prepared in the examples 1-5 AND the comparative examples 1-2 are used as electrode materials, the conductive agent AND the binder are dissolved in a solvent according to the mass percentage of 85:10:5 AND mixed, the solid content is controlled to be 50%, the mixture is coated on a copper foil current collector AND dried in vacuum, L iPF6/EC + DMC + EMC (V/V is 1:1:1) of 1 mol/L is used as electrolyte, a Celgard2400 diaphragm is adopted, a 2025 type button battery is adopted as a shell, the charge AND discharge test of the battery is carried out on a Wuhan Jinnuo electronic Co Ltd L AND battery test system, the constant current charge AND discharge are carried out at the normal temperature, the 1C is carried out, AND the charge AND discharge voltage is limited to be 0.
The test results of the composite materials prepared in examples 1 to 5 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1
As can be seen from the data in the above tables, the negative electrode materials prepared according to the methods of examples 1 to 5 are superior to the negative electrode materials prepared according to the methods of comparative examples 1 and 2 in terms of electrochemical performance such as powder compaction density, first coulombic efficiency, first reversible capacity, and the like.
In comparative example 1, the prepared composite material is not added with lithium titanate, so that the lithium titanate with higher compaction density, higher first coulombic efficiency and more excellent rate capability cannot be effectively superposed in the composite material, and further the performance of the composite material is improved. In comparative example 2, the lithium titanate nanoparticles are carbon-coated with high-temperature petroleum asphalt to obtain coated particles, which are large and cannot effectively cover the surface of hard carbon subsequently, so that the composite material cannot effectively exert the characteristic of high first coulombic efficiency of lithium titanate.
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 (10)
1. The core-shell structure composite material is characterized in that the main composition of an inner core is a hard carbon material, a shell is a composite coating layer formed by compounding nano lithium titanate particles and a carbonized binder, and the nano lithium titanate particles are fixed and dispersed on the surface of the inner core by the carbonized binder.
2. The core-shell structure composite material according to claim 1, wherein the hard carbon material is prepared by using a plant raw material as a carbon source, and the shape of the hard carbon material is any 1 or a combination of at least 2 of a sheet shape, a block shape, a sphere shape or a spherical shape;
preferably, the plant-based raw material comprises any 1 or combination of at least 2 of rice hulls, corn cobs, fruit shells or herbaceous plant stems;
preferably, the median particle diameter of the inner core is 0.5 to 30 μm, preferably 3 to 25 μm, and more preferably 5 to 18 μm;
preferably, the nano lithium titanate particles are in the shape of any 1 or a combination of at least 2 of sheets, blocks, spheres or spheres;
preferably, the median particle size of the nano lithium titanate particles is 25nm to 1000nm, preferably 25nm to 600nm, and more preferably 25nm to 300 nm.
3. Core-shell structure composite material according to claim 1 or 2, wherein the binder comprises any 1 or a combination of at least two of asphalt, epoxy resin, phenolic resin, furfural resin, urea resin or acrylic resin, preferably asphalt, further preferably any 1 or a combination of at least 2 of medium temperature coal asphalt, medium temperature petroleum asphalt, high temperature coal asphalt, high temperature petroleum asphalt or emulsified petroleum asphalt;
preferably, the carbonized binder has a carbon content of 40% or more.
4. The core-shell structure composite material according to any one of claims 1 to 3, wherein the core-shell structure composite material contains 1 to 40 wt% of nano lithium titanate particles, 30 to 80 wt% of hard carbon material, and 5 to 40 wt% of carbonized binder, based on 100 wt% of the total mass of the core-shell structure composite material;
preferably, the core-shell structure composite material contains 1 wt% -25 wt% of nano lithium titanate particles, 55 wt% -80 wt% of hard carbon material and 5 wt% -20 wt% of carbonized binder;
preferably, the median particle diameter of the core-shell structure composite material is 0.5 to 40 μm, preferably 5 to 25 μm.
5. A method of preparing a core-shell structured composite material according to any of claims 1 to 4, characterized in that the method comprises the steps of:
(1) preparing a hard carbon material as a core;
(2) the method comprises the following steps of (1) adopting nano lithium titanate particles, a binder and an inner core as raw materials, and fixing the nano lithium titanate on the surface of the inner core through the curing action of the binder to obtain a product consisting of the inner core and a composite coating layer precursor coated on the surface of the inner core;
(3) pre-sintering, and then sintering to obtain the core-shell structure composite material.
6. The method according to claim 5, wherein step (1) comprises in particular:
crushing, carbonizing and crushing plant raw materials to obtain a hard carbon material;
preferably, crushing to a median particle size of 0.5mm to 5 mm;
preferably, the carbonization temperature is 500-650 ℃, and the time is 0.5-3 h;
preferably, the pulverization is a jet pulverization, and further a pulverization is carried out to a median particle diameter of 0.5 to 30 μm, preferably 3 to 25 μm, and more preferably 5 to 18 μm.
7. The method of claim 5 or 6, wherein the method of step (2) is any 1 or 2 combination of a liquid phase coating method or a solid phase coating method;
preferably, the liquid phase coating method is any one of the first mode or the second mode,
the first mode comprises the following steps: dispersing nano lithium titanate particles and a binder in an organic solvent to obtain slurry, then placing the core obtained in the step (1) in the slurry, and reacting in a rotary evaporator to obtain a product consisting of the core and a composite coating layer precursor coated on the surface of the core;
the second mode includes: directly dispersing nano lithium titanate particles, a binder and the core obtained in the step (1) in an organic solvent, and reacting in a rotary evaporator to obtain a product consisting of the core and a composite coating layer precursor coated on the surface of the core;
preferably, in the liquid phase coating method, the dispersion is performed by: adding nano lithium titanate particles and a binder into an organic solvent, placing the organic solvent in a rotary evaporator, and rotating until slurry is completely and uniformly dispersed to obtain slurry;
preferably, in the liquid phase coating method, the first substance is dispersed in an organic solvent, and a dispersant is further included;
preferably, in the liquid phase coating method, the substance dispersed in the organic solvent further includes a dispersant;
preferably, the dispersant of mode one and mode two is independently any 1 or a combination of at least 2 of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexylphosphoric acid, sodium lauryl sulfate, methylpentanol, cellulose derivatives, polyacrylamide, guar gum, polyethylene glycol ester of fatty acid, cetyltrimethylammonium bromide, polyethylene glycol p-isooctylphenyl ether, polyacrylic acid, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate, p-ethylbenzoic acid, or polyetherimide;
preferably, in the first mode and the second mode, the mass ratio of the added dispersing agent is 0.1% -3%, preferably 0.2% -1.5% of the total weight of the inner core and the lithium titanate;
preferably, the organic solvents of mode one and mode two are independently any 1 or a combination of at least 2 of alcohols, ketones or ethers;
preferably, the first and second modes further comprise a step of cooling after the reaction is completed;
preferably, the solid phase coating method comprises: placing the nano lithium titanate particles, the binder and the core obtained in the step (1) into a fusion machine for fusion to obtain a product consisting of the core and a composite coating layer precursor coated on the surface of the core;
preferably, in the solid phase coating method, the rotating speed of the fusion machine is 500r/min to 3000r/min, and the width of the cutter gap is 0.01cm to 0.5 cm;
preferably, in the solid-phase coating method, the fusion time is not less than 0.5 h.
8. The method of any one of claims 5-7, wherein the pre-sintering of step (3) is performed under the protection of a protective gas comprising any 1 or a combination of at least 2 of nitrogen, helium, neon, argon, or xenon;
preferably, the temperature of the pre-sintering in the step (3) is 200-500 ℃;
preferably, in the step (3), the heating rate of heating to the pre-sintering temperature is 0.5-20 ℃/min, preferably 2-5 ℃/min;
preferably, the pre-sintering time in the step (3) is 0.5 to 10 hours, preferably 0.5 to 5 hours;
preferably, the sintering of step (3) is performed under the protection of a protective gas, wherein the protective gas comprises any 1 or at least 2 combinations of nitrogen, helium, neon, argon or xenon;
preferably, the sintering temperature in the step (3) is 600-1200 ℃;
preferably, in the step (3), the heating rate of heating to the sintering temperature is 0.5-20 ℃/min, preferably 2-5 ℃/min;
preferably, the sintering time in the step (3) is 0.5 to 10 hours, preferably 0.5 to 5 hours;
preferably, the reactor for performing the pre-sintering and sintering of step (3) is independently any one of a vacuum furnace, a box furnace, a rotary furnace, a roller kiln, a pusher kiln and a tube furnace.
9. The method according to any one of claims 5 to 8, wherein the inner core obtained in step (1) is subjected to a sieving step to remove large particles before being subjected to step (2) as a raw material;
preferably, the method further comprises the step of performing demagnetization, purification and screening treatment after the step (3) of pre-sintering and before the sintering treatment, wherein the screening treatment removes large particles.
10. A lithium ion battery, characterized in that the negative electrode of the lithium ion battery comprises the core-shell structure composite material according to any one of claims 1 to 4 as a negative electrode active material.
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