CN108155353B - Graphitized carbon coated electrode material, preparation method thereof and application of graphitized carbon coated electrode material as energy storage device electrode material - Google Patents
Graphitized carbon coated electrode material, preparation method thereof and application of graphitized carbon coated electrode material as energy storage device electrode material Download PDFInfo
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Abstract
The invention discloses a graphitized carbon-coated electrode material, a preparation method thereof and application of the graphitized carbon-coated electrode material as an electrode material of an energy storage device; the material is formed by coating an electrode material with graphitized carbon, and the preparation method comprises the steps of placing a mixed material of an organic matter and the electrode material or a precursor of the electrode material in a protective atmosphere, and calcining at the temperature of 800-2000 ℃ to obtain the graphitized carbon-coated electrode material. The method has the advantages of strong operability, simple process, low cost, high yield and universality, can efficiently improve the energy storage performance of the electrode material, and is suitable for commercial production.
Description
Technical Field
The invention relates to a modified electrode material, in particular to a graphitized carbon coated electrode material, a preparation method thereof and application of the graphitized carbon coated electrode material as an electrode material of an energy storage device, and belongs to the technical field of energy storage.
Background
Carbon materials, particularly graphitized carbon, have a layered structure similar to graphene and excellent electrical conductivity, and are considered to be ideal materials for improving the electron transport rate of other electrode materials.
In order to improve the conductivity of the electrode material, the conventional method is to reactCarbon components such as acetylene black, carbon nanotubes or graphene are directly added into the system to obtain the composite electrode material, but the materials cannot realize uniform coating or uniform growth on the surface of the carbon material, and have the phenomena of non-uniform dispersion and agglomeration; in addition, the interface between the ex-situ formed composite material carbon matrix and the electrode material is not tightly connected, and the interface is easy to separate and split after the charge and discharge of the electrode material are repeatedly cycled, so that the long cycle performance and the rate performance of the battery material are influenced. Secondly, amorphous carbon, although capable of in situ synthesis with electrode materials to form a uniform carbon-coated electrode material, does not provide conductivity that is comparable to that of graphitized carbon. Therefore, the preparation of graphitized carbon and the in-situ synthesis of electrode materials have attracted much attention in recent years. For example, Zhao Dongyuan academy reports graphitized carbon-coated titanium dioxide (TiO) obtained by pyrolysis of glucose and titanium dioxide electrode precursors2) Hollow spheres, the composite material exhibiting excellent lithium storage properties [ J.Am.chem.Soc.2015,137,13161-13166](ii) a Meanwhile, the American Atlantic laboratory also reports that the nickel oxide (NiO) composite material uniformly coated with graphitized carbon obtained by the high-temperature pyrolysis of Ni-MOF has the overlong high-rate sodium storage cycle performance [ ACS nano,2015,10(1):377-386]. In addition, nitrogen and sulfur doped or co-doped graphitized carbon is easily prepared from heteroatom aromatic organic matters and derivatives thereof through pyrolysis, the electron transfer rate of the electrode material can be improved, the energy storage performance of the body material is improved, and the graphitized carbon can be used as an excellent energy storage material.
Disclosure of Invention
The method aims at solving the problems that the existing carbon material coated modified electrode material is uneven in coating and easy to agglomerate, the interface connection between the carbon material and the electrode material is not tight, the carbon material is easy to separate and split, the graphitization degree of the carbon material is low, the conductivity is poor and the like.
The first purpose of the invention is to provide a modified electrode material which is coated with high-graphitization carbon in situ and has the advantages of good dispersibility and stability, high electrochemical activity and the like.
The second purpose of the invention is to provide a method for preparing the graphitized carbon-coated electrode material, which has the advantages of simple steps, strong operation controllability and low cost, and is beneficial to industrial production.
The third purpose of the invention is to provide the application of the graphitized carbon-coated electrode material, and the graphitized carbon-coated electrode material is applied to an energy storage device as an electrode material, so that the capacity and the rate capability of the energy storage device can be improved, and the service life of the energy storage device can be prolonged.
In order to achieve the technical purpose, the invention provides a preparation method of a graphitized carbon-coated electrode material, which comprises the steps of placing a mixed material of an organic matter and an electrode material or an electrode material precursor in a protective atmosphere, and calcining at 800-2000 ℃; the mixed material at least comprises at least one metal element of iron, titanium, copper, cobalt and nickel.
In a preferred embodiment, the organic material includes C6～C16Alkane, C5～C11Alcohol compound of (1), C7～C15At least one of aromatic compound, aromatic heterocyclic compound, saccharide compound, cellulose, polyacrylonitrile, polyvidone, polyvinyl chloride, polyethylene glycol, polyvinylidene fluoride, and polyacrylic acid. Saccharide compounds such as sucrose, starch, glucose, etc.
In a more preferred embodiment, the organic material is selected from C6～C16Alkane and C5～C11The alcohol compound consists of 1: 10-10: 1 by volume ratio, C6～C16The alkane of (1) includes n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane and isomers of the above alkanes. C5～C11The alcohol compound comprises n-amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, n-decyl alcohol, n-undecyl alcohol, n-dodecyl alcohol, n-tridecyl alcohol, n-tetradecyl alcohol, n-pentadecyl alcohol and isomers of the above alcohols. In a further preferable scheme, the organic matter is composed of n-hexane and n-pentanol according to a volume ratio of 1-10: 1. The optimal ratio is that n-hexane and n-pentanol are mixed according to the ratio of 6: 1. The preferred organic matter is mainly liquid organic matter, and can be well combined with electrode materialThe main advantages of the combination of alkanes and alcohols are represented by the following: on one hand, the carbonization and graphitization are carried out by combining the two, the yield of the carbonization and graphitization product is high, the graphitization degree of the coating carbon material is high, high-purity graphitized carbon is easier to obtain, and the performances of conductivity, capacity and the like of the coating material are improved.
Preferably, the electrode material comprises a known positive electrode material or a known negative electrode material. The preferable anode electrode material comprises the three-component materials of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate, nickel cobalt manganese lithium and the like which are already marketed and a lithium/sodium-rich layered compound, and the molecular general formula is AxMO2(A ═ Li, Na; M ═ Fe, Cr, V, etc.) and a transition metal oxide of the general molecular formula XOm n-(such as X-P, S), and has a molecular formula of AxM2(PO4)3And (A ═ Li, Na; M ═ V, Fe, Ti) polyanion compounds of NASICON type. Preferred negative electrode materials include all types of carbon-based materials including graphite negative electrode materials which have been industrially produced, all metal oxide and metal sulfide negative electrode materials, negative electrode materials derived from Si-based, Ge-based, Sn-based, Pb-based, P-based, As-based, Sb-based, Bi-based, etc. of the fourth and fifth main groups, and spinel-type lithium titanate and Na4Ti5O12，NaTiO2And Na2TinO2n+1(2<n<9) Titanium-based materials such as sodium titanate, titanium dioxide, titanium oxide, potassium titanate, titanic acid, titanium sulfate, titanium carbide and the like with different molecular formulas and NASICON-Na2Ti2(PO4)3And the titanium phosphate-based negative electrode material is prepared.
In a preferred embodiment, the electrode material precursor is a raw material that generates a positive electrode material or a negative electrode material by a reaction. The above-described raw materials of known positive electrode materials or negative electrode materials are all included in the selection range of the electrode material precursor. Such as elemental raw materials including elements in various positive electrode materials or negative electrode materials; or salts of various elements, such as various inorganic salts, such as halogen salts, carbonates, nitrates, sulfates, phosphates, silicates, etc.; or organic salts of various elements, such as n-butyl titanate and titanium isopropoxide.
In a preferable scheme, the calcination time is 0.5-10 h. Preferably 1-5 h.
The invention also provides a graphitized carbon-coated electrode material which is prepared by the method.
In a preferred scheme, the graphitized carbon-coated electrode material contains 5-98% of the electrode material by mass percent.
The invention also provides application of the graphitized carbon-coated electrode material as an electrode material of an electrochemical energy storage device.
The electrochemical energy accumulator comprises a super capacitor, a lithium ion battery, a solar battery, a fuel battery, a lithium air battery, a lithium sulfur battery, a lithium air battery, a sodium ion battery, a sodium sulfur battery, a sodium air battery, an aluminum ion battery or a magnesium ion battery and the like.
The carbon material in the graphitized carbon-coated electrode material can be graphitized carbon or heteroatom-doped graphitized carbon according to different selected raw materials.
In the technical scheme of the invention, the mixture of the organic matter and the electrode material or the electrode material precursor can be solid, liquid or paste, and is determined according to the selected raw materials.
According to the technical scheme, the mixed material needs to contain metal elements such as iron, titanium, copper, cobalt or nickel, and the metal elements have the function of catalyzing graphitization conversion of the carbon material, so that the appropriate content of the metal such as iron, titanium, copper, cobalt or nickel is beneficial to generation of graphitized carbon, and the graphitization degree of the graphitized carbon of the coating layer can be improved. These metals can be introduced through the electrode material, or a small amount of metal simple substances such as iron, titanium, copper, cobalt or nickel, salts or oxides, and the like are additionally added, so that the generation of graphitized carbon is facilitated. The amount of the catalyst to be added may be a catalytic amount generally used.
In the technical scheme of the invention, the protective atmosphere is at least one of argon, nitrogen or hydrogen.
In the technical scheme of the invention, the calcination temperature is required to be higher than 800 ℃, and the calcination temperature is lower than 800 ℃ to mainly obtain the amorphous carbon. And the calcination temperature is 800-2000 ℃ to mainly obtain graphitized carbon.
The thickness of the graphitized carbon of the coating layer of the electrode material in the technical scheme of the invention is determined by the amount and the type of the organic matters.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1. the graphitized carbon coated electrode material has the advantages that the graphitized carbon has high graphitization degree, uniform coating and good stability, on one hand, the carbon on the graphitized carbon layer improves the conductivity of the electrode material, greatly improves the electron transfer rate in the energy storage process, accelerates the electron dynamics process, and on the other hand, the graphitized carbon coated electrode material can contribute certain energy storage performance, thereby realizing the further development of electrochemical energy storage devices with high capacity, high multiplying power and long service life.
2. The graphitized carbon coated electrode material is obtained in situ by one step of high-temperature calcination, and graphitized carbon is formed by pyrolysis of organic matters and coated on the surface of the electrode material, so that a composite material with good dispersibility and stable coating can be obtained. The carbon coating method can greatly improve the electron dynamics process of the electrode material on one hand, and can inhibit the volume expansion of the electrode material and the direct side reaction between the electrode material and the electrolyte in the charging and discharging process on the other hand, thereby obviously improving the electrochemical energy storage performance of the electrode material and having wide reference value;
3. the preparation method of the graphitized carbon-coated electrode material has the advantages of wide raw material source, low cost, simple process, no need of filtration, centrifugal dialysis and the like, and controllable, strong and convenient operation;
4. the graphitized carbon-coated electrode material is applied to the field of electrochemical energy storage devices, and represents excellent energy storage indexes of high capacity, high power and long service life.
Drawings
FIG. 1 is a photograph of the organic material obtained in example 1, as a real object, before calcination with a titanium dioxide precursor;
fig. 2 is a scanning electron micrograph of a composite of the graphitized carbon-coated titanium dioxide electrode material obtained in example 1;
fig. 3 is a transmission electron micrograph of a composite of the graphitized carbon-coated titanium dioxide electrode material obtained in example 1;
fig. 4 is a high-power transmission electron micrograph of a composite of the graphitized carbon-coated titanium dioxide electrode material obtained in example 1;
fig. 5 is a graph showing the sodium storage cycle performance of the composite of the graphitized carbon-coated titanium dioxide electrode material obtained in example 1.
Fig. 6 is a transmission electron microscope image of a composite of the amorphous carbon-coated titanium dioxide electrode material obtained in comparative example 1.
Fig. 7 is a raman spectrum of the carbon component contained in the composite material obtained in example 1 and comparative example 1.
Fig. 8 is a transmission electron microscope image of a composite of the graphitized carbon-coated titanium dioxide electrode material obtained in example 3.
Detailed Description
The following examples are intended to illustrate the invention in more detail, and are not intended to limit the invention in any way, which can be carried out in any way as described in the summary of the invention.
Example 1
Firstly, 1.0ml of titanium chloride solution (15 percent titanium trichloride dilute hydrochloric acid solution) and a certain amount of cetyl trimethyl ammonium bromide (CTAB; 0.58g) are dissolved and uniformly dispersed in a mixed organic solvent consisting of normal hexane (60ml) and n-amyl alcohol (10ml), then the mixed organic solvent is transferred into a 100ml reaction kettle, and the mixture of an organic matter and a titanium dioxide precursor is obtained by direct vacuum drying in a 200 ℃ oven with solvent heat for 6 h. Then calcining for 2h at 800 ℃ in an inert protective gas environment, wherein the heating rate is 10 ℃/min, and naturally cooling. The obtained black powder is a composite of titanium dioxide electrode materials coated by graphitized carbon. Fig. 1 is a photo of the organic matter and titanium dioxide precursor after solvent heating, which shows that the obtained substance is white paste. Fig. 2 is a scanning electron microscope image of the prepared composite of the graphitized carbon-coated titanium dioxide electrode material, which shows that the obtained product is in the form of uniformly dispersed small particles. Fig. 3 is a transmission electron micrograph of the prepared composite of the graphitized carbon-coated titanium dioxide electrode material, which shows that the surface of the titanium dioxide particles is coated with a layer of material. Fig. 4 is a high power transmission electron micrograph of a composite of a titanium dioxide electrode material coated with graphitized carbon, showing that the surface of the titanium dioxide particles is coated with graphitized carbon material having 3 to 10 layers of coating material.
The obtained graphitized carbon-coated titanium dioxide electrode material composite is used as a sodium ion battery negative electrode material, slurry is prepared according to the mass ratio of active substances to acetylene black as a conductive agent to sodium carboxymethyl cellulose as a binder of 70:15:15, the slurry is coated on copper foil and dried to obtain an electrode pole piece, and the electrode pole piece is assembled into a CR2016 type button battery in a glove box after being cut and weighed, so that the electrochemical sodium storage performance of the composite material is researched. As shown in FIG. 5, at 0.25C (83.75mA g)-1) The specific discharge capacity after 200 charge-discharge cycles is 189.5mAh g under the current density of (1)-1And the charging specific capacity is 188.8mAh g-1And the sodium storage capacity is better.
Comparative example 1
Calcining at a lower temperature.
Firstly, 1.0ml of titanium chloride solution (15 percent titanium trichloride dilute hydrochloric acid solution) and a certain amount of cetyl trimethyl ammonium bromide (CTAB; 0.58g) are dissolved and uniformly dispersed in a mixed organic solvent consisting of normal hexane (60ml) and n-amyl alcohol (10ml), then the mixed organic solvent is transferred into a 100ml reaction kettle, and the mixture of an organic matter and a titanium dioxide precursor is obtained by direct vacuum drying in a 200 ℃ oven with solvent heat for 6 h. Then calcining for 2h at 500 ℃ in an inert protective gas environment, wherein the heating rate is 10 ℃/min, and naturally cooling. Black powder of the amorphous carbon-coated titanium dioxide electrode material was obtained. Fig. 6 is a transmission electron micrograph of the prepared amorphous carbon-coated titanium dioxide electrode material composite, showing that the titanium dioxide particle coating layer is amorphous carbon. FIG. 7 shows the complexes obtained in example 1 and comparative example 1Raman spectrum of carbon component coated in the composite material. The intensity of the D peak is related to sp3 hybridized bonds of disordered carbon, sp3 hybridized bonds of a regular tetrahedron structure and sp3 hybridized defects at the edge of graphene, the intensity of the G peak is related to sp2 hybridized bonds of a plane body structure, and sp2 hybridized carbon planes are stacked layer by layer to form a graphite structure. In general, with IDKey/IG bondThe ratio of (a) to (b) represents the degree of graphitization and disorder of the carbon component. As can be seen from FIG. 7, I in the carbon component of the composite calcined at 500 ℃ isD key/IG bondA ratio of (A) to (B) of greater than 1 indicates that the carbon component exhibits predominantly an amorphous structure, whereas I in the carbon component of the 800 ℃ calcined composite materialD key/IGThe bond ratio is less than 1 and is obviously less than the D, G peak strength ratio of the composite material calcined at 500 ℃, which shows that the graphitization degree of the carbon coating obtained by the calcination at 800 ℃ is very high.
The obtained amorphous carbon-coated titanium dioxide electrode material composite is used as a sodium ion battery negative electrode material, slurry is prepared according to the mass ratio of active substances to acetylene black serving as a conductive agent to sodium carboxymethyl cellulose serving as a binder being 70:15:15, the slurry is coated on copper foil and dried to obtain an electrode piece, the electrode piece is assembled into a CR2016 type button battery after being cut and weighed, and the electrochemical sodium storage performance of the composite material is researched. At 0.25C (83.75mA g)-1) The specific discharge capacity after 100 charge-discharge cycles is 142.5mAh g under the current density of (1)-1The charging specific capacity is 141.8mAh g-1A slightly inferior sodium storage capacity is exhibited, which may be due to the limited conductivity of the amorphous carbon coating layer.
Example 2
Firstly, 1.0ml of titanium chloride solution (15 percent titanium trichloride dilute hydrochloric acid solution) and a certain amount of cetyl trimethyl ammonium bromide (CTAB; 0.58g) are dissolved and uniformly dispersed in a mixed organic solvent consisting of normal hexane (60ml) and n-amyl alcohol (10ml), then the mixed organic solvent is transferred into a 100ml reaction kettle, and the mixture of an organic matter and a titanium dioxide precursor is obtained by direct vacuum drying in a 200 ℃ oven with solvent heat for 6 h. Then calcining for 2h at 900 ℃ in an inert protective gas environment, wherein the heating rate is 10 ℃/min, and naturally cooling. Obtaining black powder of the titanium dioxide electrode material coated by the graphitized carbon.
The obtained graphitized carbon-coated titanium dioxide electrode material composite is used as a sodium ion battery negative electrode material, slurry is prepared according to the mass ratio of active substances to acetylene black as a conductive agent to sodium carboxymethyl cellulose as a binder of 70:15:15, the slurry is coated on copper foil and dried to obtain an electrode pole piece, and the electrode pole piece is assembled into a CR2016 type button battery in a glove box after being cut and weighed, so that the electrochemical sodium storage performance of the composite material is researched. At 0.25C (83.75mA g)-1)、0.5C(167.5mA g-1)、1C(335mA g-1)、2.5C(670mA g-1).5C(1675mA g-1)、7.5C(1675mA g-1) Respectively has a reversible charging specific capacity of 190.7mAh g under different current densities-1、180.mAh g-1、171.4mAh g-1、142.4mAh g-1、120.5mAh g-1、93.1mAh g-1And the better sodium storage rate performance is shown.
Example 3
Firstly, 1.0ml of titanium chloride solution (15% titanium trichloride diluted hydrochloric acid solution) and a certain amount of cetyl trimethyl ammonium bromide (CTAB; 0.58g) are dissolved and uniformly dispersed in a mixed organic solvent consisting of normal hexane (60ml) and n-hexanol (10ml), then the mixed organic solvent is transferred into a 100ml reaction kettle, and the mixture of an organic matter and a titanium dioxide precursor is obtained by direct vacuum drying in a 200 ℃ oven with solvent heat for 6 h. Then calcining for 2h at 800 ℃ in an inert protective gas environment, wherein the heating rate is 10 ℃/min, and naturally cooling. Obtaining black powder of the titanium dioxide electrode material coated by the graphitized carbon. Fig. 8 is a transmission electron micrograph of the prepared composite of the graphitized carbon-coated titanium dioxide electrode material, showing that the titanium dioxide particle coating layer is a graphitized carbon structure, but the graphitization degree is not as obvious as that of example 1.
Taking the obtained graphitized carbon-coated titanium dioxide electrode material composite as a sodium ion battery negative electrode material, mixing the cathode material with a slurry according to the mass ratio of active substances to acetylene black as a conductive agent to sodium carboxymethyl cellulose as a binder of 70:15:15, coating the slurry on a copper foil, drying the slurry to obtain an electrode pole piece, weighing cut pieces, assembling the cut pieces into a CR2016 type button battery in a glove box, and exploring the electrochemical storage capacity of the composite materialSodium property. At 0.25C (83.75mA g)-1) The first charge-discharge specific capacity is 186.2mAh g respectively under the current density of (1)-1And 461.4mAh g-1The first coulombic efficiency is 40.35%, and the sodium storage reversibility is good.
Example 4
Firstly, 357mg of cobalt chloride hexahydrate solution and a certain amount of hexadecyl trimethyl ammonium bromide (CTAB; 0.58g) are dissolved and uniformly dispersed in a mixed organic solvent consisting of n-hexane (60ml) and n-pentanol (10ml), then the mixed organic solvent is transferred into a 100ml reaction kettle, and the mixture of an organic matter and a titanium dioxide precursor is obtained by directly vacuum drying the mixed organic solvent in a drying oven with the temperature of 200 ℃ for 6 h. Then calcining for 2h at 800 ℃ in an inert protective gas environment, wherein the heating rate is 10 ℃/min, and naturally cooling. Obtaining the graphitized carbon-coated cobalt oxide composite electrode material.
The obtained compound of the graphitized carbon-coated cobalt oxide electrode material is used as a lithium ion battery negative electrode material, the active material, the conductive agent acetylene black and the binder carboxymethylcellulose sodium are mixed into slurry according to the mass ratio of 70:15:15, the slurry is coated on a copper foil and dried to obtain an electrode pole piece, the electrode pole piece is assembled into a CR2016 type button cell in a glove box after being cut and weighed, and the electrochemical lithium storage performance of the compound material is researched. At 200mA g-1Under the current density of (A), the specific discharge capacity of the lithium ion battery after 100 charge-discharge cycles is 919.2mAh g-1The charging specific capacity is 901.3mAh g-1And the lithium storage performance is better.
Example 5
Firstly, 1.0ml of titanium chloride solution (15 percent titanium trichloride dilute hydrochloric acid solution) and a certain amount of cetyl trimethyl ammonium bromide (CTAB; 0.58g) are dissolved and uniformly dispersed in a mixed organic solvent consisting of normal hexane (60ml) and n-amyl alcohol (10ml), then the mixed organic solvent is transferred into a 100ml reaction kettle, and the mixture of an organic matter and a titanium dioxide precursor is obtained by direct vacuum drying in a 200 ℃ oven with solvent heat for 6 h. Then calcining for 2h at 850 ℃ in an inert protective gas environment, wherein the heating rate is 10 ℃/min, and naturally cooling. Obtaining black powder of the titanium dioxide electrode material coated by the graphitized carbon.
The obtained graphitized carbon coated titanium dioxide is chargedThe composite of the pole materials is used as a lithium ion battery cathode material, the active material, the conductive agent acetylene black and the binder carboxymethylcellulose sodium are mixed into slurry according to the mass ratio of 70:15:15, the slurry is coated on copper foil and dried to obtain an electrode pole piece, the electrode pole piece is assembled into a CR2016 type button cell in a glove box after being weighed, and the electrochemical lithium storage performance of the composite material is researched. At 0.5C (167.5mA g)-1) The specific discharge capacity after 100 charge-discharge cycles is 210.8mAh g under the current density of (1)-1The charging specific capacity is 209.6mAh g-1And the electrochemical lithium storage performance is better.
Claims (8)
1. A preparation method of graphitized carbon-coated electrode material is characterized by comprising the following steps: placing a mixed material of an organic matter and an electrode material or an electrode material precursor in a protective atmosphere, and calcining at 800-2000 ℃ to obtain the composite material;
the mixed material contains at least one metal element of iron, titanium, copper, cobalt and nickel; the organic matter is composed of C6~C16Alkane and C5~C11The alcohol compound consists of 1: 10-10: 1 by volume ratio.
2. The method for preparing a graphitized carbon-coated electrode material according to claim 1, characterized in that: the organic matter is composed of n-hexane and n-pentanol according to the volume ratio of 1-10: 1.
3. The method for preparing a graphitized carbon-coated electrode material according to any one of claims 1 to 2, characterized in that:
the electrode material comprises a positive electrode material or a negative electrode material;
the anode electrode material comprises at least one of lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate and nickel cobalt manganese lithium, or AxMO2A = Li and/or Na, M = at least one of Fe, Cr, V, or AxM2(PO4)3A = Li and/or Na, M = V, Fe, Ti;
the negative electrode material comprises a carbon substrateMaterial, silicon material, metal oxide, metal sulfide, spinel type lithium titanate, Na4Ti5O12、NaTiO2、Na2TinO2n+1Titanium carbide and Na2Ti2(PO4)3At least one of (1); therein, 2<n<9。
4. The method for preparing a graphitized carbon-coated electrode material according to any one of claims 1 to 2, characterized in that:
the electrode material precursor is a raw material for generating a positive electrode material or a negative electrode material through reaction.
5. The method for preparing a graphitized carbon-coated electrode material according to any one of claims 1 to 2, characterized in that: the calcination time is 0.5-10 h.
6. A graphitized carbon-coated electrode material is characterized in that: prepared by the method of any one of claims 1 to 5.
7. The graphitized carbon-coated electrode material according to claim 6, wherein: the graphitized carbon-coated electrode material comprises 5-98% of the electrode material by mass percent.
8. Use of the graphitized carbon-coated electrode material according to claim 6 or 7, characterized in that: the material is applied as an electrode material of an electrochemical energy storage device.
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| CN109616640B (en) * | 2018-12-05 | 2020-11-03 | 中南大学 | Modified microcrystalline graphite, preparation thereof and application thereof in lithium ion battery |
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| CN111082063B (en) * | 2019-12-26 | 2023-03-28 | 内蒙古民族大学 | Flexible conductive carbon/metal composite nanofiber membrane, preparation method and application thereof, and lithium-sulfur battery |
| CN112174131B (en) * | 2020-10-10 | 2022-08-09 | 福建师范大学 | Method for preparing graphitized hollow carbon composite material by dynamic catalytic wide-area graphitization |
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