CN112928246B - Composite material, preparation method and application thereof - Google Patents

Composite material, preparation method and application thereof Download PDF

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CN112928246B
CN112928246B CN201911242305.2A CN201911242305A CN112928246B CN 112928246 B CN112928246 B CN 112928246B CN 201911242305 A CN201911242305 A CN 201911242305A CN 112928246 B CN112928246 B CN 112928246B
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single crystal
lithium ion
temperature
composite material
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CN112928246A (en
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张洪章
宋子晗
李先锋
张华民
阎景旺
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Dalian Institute of Chemical Physics of CAS
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C—CHEMISTRY; METALLURGY
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    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
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    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract

The invention provides a composite material, a preparation method and application thereof, wherein the composite material is a nano carbon layer coated single crystal H-Nb 2 O 5 Wherein the core is single crystal H-Nb 2 O 5 The particles have a longest dimension of 2 to 10 μm, and a shell of 10 to 20nm thick comprising a carbon nanocarbon layer. The nano carbon layer coated single crystal H-Nb obtained by the preparation method of the invention 2 O 5 The composite material has reversible capacity of 270 mAh/g; and single crystal of H-Nb 2 O 5 The nano carbon layer has intrinsic high lithium ion diffusion capacity, the uniform nano carbon layer improves the electronic conductivity of the material, the ultrahigh multiplying power charge-discharge capacity and the long cycle stability of the material are ensured, and the nano carbon layer coated single crystal H-Nb 2 O 5 Has proper lithium intercalation potential, does not generate lithium precipitation under high current density, and therefore, has good safety.

Description

Composite material, preparation method and application thereof
Technical Field
The invention relates to a single crystal H-Nb 2 O 5 The technical field of materials, in particular to a composite material, a preparation method and application thereof.
Background
With continuous innovation of terminal application technology and increase of market demand, development of higher energy storage equipment is imperative, and especially, development of an energy storage technology which has high capacity, can be charged and discharged quickly and has good safety is imperative. Lithium ion batteries and lithium ion capacitors are currently the most common high rate energy storage technologies. The electrode material is the main body of energy storage, and directly determines the comprehensive performance of an energy storage battery or a capacitor, so the optimization and innovation of the electrode key material are the key for improving the performance. The properties of the negative electrode material directly affect the power performance and safety performance of the energy storage battery or capacitor.
For lithium ion batteries, graphite negative electrodes are the most common negative electrode materials of the current commercial lithium ion batteries, the theoretical specific capacity of the graphite negative electrodes is 372mAh/g, and the graphite negative electrodes have low lithium intercalation potential (<0.2V，vs.Li + /Li). However, at high current density, the graphite negative electrode has an increased lithium intercalation overpotential, which may cause a risk of lithium precipitation and a battery circuit to cause a battery safety problem, and therefore, it is not suitable for high-rate charge and discharge. Lithium titanate (Li) 4 Ti 5 O 12 LTO) negative electrode lithium intercalation potential is 1.55V (vs. Li) + Li), the volume should be reduced in the charging and discharging process, and the lithium ion battery is a negative electrode material which has high safety, long service life and can be charged and discharged rapidly. However, due to its high potential and low specific capacity (175mAh/g), it is difficult to satisfy the demand for high specific energy batteries with energy density. The silicon-based composite negative electrode material is a novel high-specific-capacity negative electrode, the actual specific capacity of the silicon-based composite negative electrode material can reach 600-2000mAh/g, and good high-rate charge and discharge performance can be realized through nanocrystallization of the material. However, the inherent huge volume expansion of the material in the lithium intercalation process affects the cycle life of the material, and the problems of low coulomb charge and discharge for the first time, complex material manufacturing process and the like exist, which make the large-scale practical application of the silicon-based negative electrode difficult to realize. The lithium ion capacitor is used for storing lithium rapidly by adsorption and desorptionThe properties enable high rate charging and discharging, but their capacity is limited. The energy density of the hybrid capacitor formed by the traditional capacitor anode material and the high-rate oxidation-reduction cathode material can be effectively improved. Therefore, exploring a suitable negative electrode material is a hotspot and difficulty in developing the next generation of high-rate and high-safety energy storage technology.
Disclosure of Invention
Based on the defects of lithium ion battery cathode material in the prior art such as lithium separation, low energy density, short cycle life, limited capacity of a lithium ion capacitor and the like, the invention provides a composite material which can be used as a cathode for a lithium ion battery and a lithium ion capacitor and is a nano carbon layer coated single crystal H-Nb 2 O 5 Has proper lithium intercalation potential, high reversible capacity and good safety.
Single crystal H-Nb in the present application 2 O 5 Is Nb 2 O 5 A variant of (A), Nb 2 O 5 The crystal structure of (2) is related to the preparation method.
According to one aspect of the application, a composite material is provided, and the composite material is a nano carbon layer coated single crystal H-Nb 2 O 5 Wherein the core is single crystal H-Nb 2 O 5 The particles have a longest dimension of 2 to 10 μm, and a shell of 10 to 20nm thick comprising a carbon nanocarbon layer.
Optionally, the nano carbon layer coats the single crystal H-Nb 2 O 5 The content of the medium carbon is 2.0-4.0 wt%.
Preferably, the nano carbon layer coats the single crystal H-Nb 2 O 5 The content of the medium carbon is 2.5-3.5 wt%.
The application also prepares a preparation method of the composite material, which at least comprises the following steps:
a) obtaining single crystal H-Nb 2 O 5 ；
b) Will contain single crystal H-Nb 2 O 5 Reacting with a mixture of a carbon source, and carbonizing to obtain the nano carbon layer coated single crystal H-Nb 2 O 5 。
Optionally, the single crystal H-Nb in step a) 2 O 5 The obtaining method comprises the following steps: calcining a raw material containing a niobium source to obtain the single crystal H-Nb 2 O 5 。
Optionally, the niobium source comprises at least one of niobium carbide, niobium hydroxide, niobium oxalate, niobium pentachloride, niobium ethoxide, niobium dioxide, niobium monoxide, and lithium niobate.
Alternatively, the conditions of the calcination are: the reaction temperature is 900-1200 ℃; the reaction time is 6-24 h.
Optionally, the carbon source comprises at least one of dopamine, methoxypolyethylene glycol-dopamine, and thiol-polyethylene glycol-dopamine.
Alternatively, the reaction is a polymerization reaction.
Optionally, the carbon source and the single crystal of H-Nb in step b) 2 O 5 The mass ratio of (A) to (B) is 1: 10-1: 4.
Preferably, the carbon source is reacted with the single-crystal H-Nb in step b) 2 O 5 The mass ratio of (A) to (B) is 1: 8-1: 6.
Optionally, the reaction time is 6-48 h.
Preferably, the reaction time is 12-16 h.
The carbonization treatment conditions commonly used can be used in the present application, and those skilled in the art can select appropriate reaction conditions according to actual production needs. Preferably, the carbonization treatment conditions are: the reaction temperature is 800-1000 ℃; the reaction temperature rise speed is 1-5 ℃/min; the reaction time is 2-6 h.
Optionally, the carbonization is performed under an inert atmosphere.
Optionally, the inert atmosphere comprises an inert atmosphere and a nitrogen atmosphere.
The temperature reduction conditions after the carbonization treatment can be commonly used in the present application, and a person skilled in the art can select appropriate reaction conditions according to the actual production needs. Preferably, the temperature is reduced after the carbonization treatment is finished, and the temperature reduction rate is 1-10 ℃/min.
The obtaining of said mixture in step b) comprises at least the following steps: will contain single crystal H-Nb 2 O 5 And mixing the dispersion liquid with a solution containing a carbon source to obtain the mixture.
Alternatively, the single crystal H-Nb 2 O 5 The solid content of the dispersion is 0.05-5.0 wt%.
Preferably, the single crystal H-Nb 2 O 5 The solid content of the dispersion is 0.5-2 wt%.
Optionally, the single crystal of H-Nb 2 O 5 The dispersion of (a) includes a solution buffer; the solution buffer comprises at least one of Tris hydrochloride (Tris), potassium dihydrogen phosphate and sodium dihydrogen phosphate.
Optionally, the pH of the dispersant is 8-9.
Optionally, a solvent is included in the solution; the solvent comprises at least one of water, methanol, ethanol, propanol and glycol.
Optionally, the concentration of the solution is 0.05-0.5 mol/L.
Optionally, the step B) comprises at least the following steps:
(1) adding a solution containing a carbon source to a solution containing single crystal H-Nb under stirring 2 O 5 Stirring and polymerizing to obtain the carbon precursor coated monocrystal H-Nb 2 O 5 ；
(2) Single crystal H-Nb coated with the carbon precursor 2 O 5 Carbonizing to obtain the composite material.
Preferably, said step b) comprises at least the following steps: continuously stirring the single crystal H-Nb 2 O 5 Dispersing while slowly adding dopamine solution to the single crystal H-Nb 2 O 5 Adding the dispersion at a speed of 20-100 mL/min; continuously stirring the mixed solution for 6-48H after adding, carrying out polymerization reaction on dopamine monomer, washing, separating and drying to obtain poly-dopamine-coated monocrystal H-Nb 2 O 5 。
Optionally, the solvent used for washing is at least one of water, methanol, ethanol and propanol.
The common drying conditions can be used in the present application, and those skilled in the art can select suitable reaction conditions according to the actual production needs. Preferably, the drying treatment temperature is 70-100 ℃, and the treatment time is 12-48 h.
Optionally, the step of carbonizing includes at least: coating the obtained carbon precursor with single crystal H-Nb 2 O 5 Placing the mixture in a tube furnace with inert atmosphere for high-temperature carbonization treatment to obtain nano carbon layer coated single crystal H-Nb 2 O 5 The composite material of (1).
Optionally, the single crystal of H-Nb 2 O 5 The preparation method of the dispersion liquid comprises the following steps: mixing single crystal H-Nb 2 O 5 And uniformly dispersing the mixture in Tris buffer aqueous solution by ultrasonic for 15-60 minutes to obtain the finished product.
The application also provides a negative electrode material, which comprises at least one of the composite material and the composite material prepared by the method.
The application also provides a lithium ion battery which comprises at least one of the composite material, the composite material prepared by the method and the negative electrode material.
In addition, the application provides a lithium ion capacitor, which comprises at least one of the composite material, the composite material prepared by the method and the negative electrode material.
The beneficial effect that this application can produce includes:
1) the nano carbon layer coated single crystal H-Nb prepared by the preparation method of the invention 2 O 5 Compared with Nb prepared by the conventional preparation method 2 O 5 Has a reversible capacity of up to 270 mAh/g;
2) single crystal H-Nb 2 O 5 The material has intrinsic high lithium ion diffusion capacity, the uniform nano carbon layer improves the electronic conductivity of the material, and the ultrahigh-rate charge and discharge capacity and long cycle stability of the material are ensured;
3) nano carbon layer coated single crystal H-Nb 2 O 5 Has proper lithium intercalation potential, does not generate lithium precipitation under high current density, and therefore, has good safety.
Drawings
FIG. 1 shows a single crystal H-Nb coated with a nano carbon layer obtained in example 1 2 O 5 XRD pattern of (a);
FIG. 2 shows a single crystal H-Nb coated with a nano carbon layer obtained in example 1 2 O 5 A TEM image of (B);
FIG. 3 shows a single crystal H-Nb coated with a nano carbon layer obtained in example 1 2 O 5 SEM picture of (1);
FIG. 4 shows a single crystal H-Nb coated with a nano carbon layer obtained in example 1 2 O 5 Charge and discharge curves at 0.25C;
FIG. 5 shows a single crystal H-Nb coated with a nano carbon layer obtained in example 1 2 O 5 A material rate performance graph;
FIG. 6 shows a single crystal H-Nb coated with the nano carbon layer obtained in example 1 2 O 5 Material 1000 cycle performance plots.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The SEM test adopts a scanning electron microscope/JSM-7800F instrument;
the XRD test adopts an X-ray powder diffractometer/RigakuUltima IV;
the TEM test adopts an instrument of an environmental projection electron microscope/Titan Themis ETEM G3;
the TGA test adopts an instrument of thermogravimetric analyzer/PYRIS Diamond;
the battery for the battery performance test is a CR2016 type button battery, and the adopted instrument is a blue battery test system/CT 2001A.
Example 1
Single crystal H-Nb 2 O 5 Preparation of (1 #):
putting the corundum crucible filled with 5g of niobium carbide into a muffle furnace, and heating to 1000 ℃ at the heating rate of 2 ℃/min; keeping the temperature for heat treatment for 12H, and then cooling to room temperature at the speed of 10 ℃/min to obtain the single crystal H-Nb 2 O 5 (1#)；
Preparation of sample material (a 1):
1g of the obtained single crystal H-Nb was weighed 2 O 5 (1#) material was uniformly dispersed in Tris buffer aqueous solution with pH 8.5 by ultrasonic treatment for 30 minutes, and single crystal H-Nb was continuously stirred 2 O 5 (1#) dispersion; weighing 0.36g of dopamine, and dissolving the dopamine in 10mL of deionized water to prepare a dopamine solution; dropwise adding the obtained dopamine solution into the stirred monocrystal H-Nb 2 O 5 (1#) the dispersion liquid is continuously stirred for 24 hours, and dopamine is subjected to polymerization reaction on the surface of the material; after the polymerization reaction is finished, washing the mixture by using ethanol for three times, performing centrifugal separation to obtain a product, and drying the product in an oven for 12 hours at 90 ℃; and transferring the dried product to a porcelain boat, putting the porcelain boat into a tubular furnace, heating to 850 ℃ at a speed of 5 ℃/min in an argon atmosphere, preserving the heat for 2h, and cooling to room temperature at a speed of 5 ℃/min after the carbonization reaction is finished to obtain the composite sample material (A1).
Preparation of half-cell (B1):
preparing an electrode using the sample material (a1) as an electrode active material; the material composition of the electrode is as follows: the mass ratio of the composite material (A1), the carbon black and the PVdF is 8:1:1, the current collector is aluminum foil, the electrolyte is LBC0305, and the obtained electrode and the metal lithium form a half-cell for testing the cell performance.
Example 2
Single crystal H-Nb used in example 2 2 O 5 Namely, the single crystal H-Nb prepared in example 1 2 O 5 (1#)。
Preparation of sample material (a 2):
the preparation of the sample material (a2) differs from the preparation of the sample material (a1) in the following points: dropwise adding dopamine solution into stirred monocrystal H-Nb 2 O 5 In the case of the dispersion, the stirring duration was changed to 12 hours, and the other reaction steps and conditions were the same as in example 1.
Preparation of half-cell (B2):
the procedure and conditions for preparing a half cell (B2) from the sample material (a2) as an electrode active material were the same as in example 1.
Example 3
Single crystal H-Nb used in example 3 2 O 5 Namely, the single crystal H-Nb prepared in example 1 2 O 5 (1#)。
Preparation of sample material (a 3):
the preparation of the sample material (A3) differs from the preparation of the sample material (a1) in the following points: dropwise adding dopamine solution into stirred single crystal H-Nb 2 O 5 In the case of the dispersion, the stirring duration was changed to 48 hours, and the other reaction steps and conditions were the same as in example 1.
Preparation of half-cell (B3):
the procedure and conditions for preparing a half cell (B3) from the sample material (a3) as an electrode active material were the same as in example 1.
Example 4
Single crystal H-Nb 2 O 5 Preparation of (2 #):
putting the corundum crucible filled with 5g of niobium dioxide into a muffle furnace, and heating to 1000 ℃ at the heating rate of 2 ℃/min; keeping the temperature for heat treatment for 12H, and then cooling to room temperature at the speed of 10 ℃/min to obtain the single crystal H-Nb 2 O 5 (2#)。
Preparation of sample material (a 4):
1g of the obtained single crystal H-Nb was weighed 2 O 5 (2#) uniformly dispersed in Tris buffer aqueous solution with pH 8.5 for 30 min by ultrasonic treatment, and continuously stirring single crystal H-Nb 2 O 5 (2#) dispersion; weighing 0.36g of dopamine, and dissolving the dopamine in 10mL of deionized water to prepare a dopamine solution; dropwise adding the obtained dopamine solution into the stirred single crystal H-Nb 2 O 5 (2#) the dispersion liquid is continuously stirred for 24 hours, and dopamine is subjected to polymerization reaction on the surface of the material; washing the mixture for three times by using ethanol after the polymerization reaction is finished, performing centrifugal separation to obtain a product, and drying the product at 90 ℃ for 12 hours; and transferring the dried product to a porcelain boat, putting the porcelain boat into a tubular furnace, heating to 850 ℃ at a speed of 5 ℃/min in an argon atmosphere, preserving the heat for 2h, and cooling to room temperature at a speed of 5 ℃/min after the carbonization reaction is finished to obtain the composite sample material (A4).
Preparation of half-cell (B4):
the procedure and conditions for preparing a half cell (B4) from the sample material (a4) as an electrode active material were the same as in example 1.
Example 5
Polycrystalline Nb 2 O 5 Preparation of (3 #):
polycrystalline Nb 2 O 5 (3#) preparation method and monocrystal H-Nb 2 O 5 (2#) was prepared except that niobium hydroxide was used and other reaction steps and conditions were the same as in example 4.
Preparation of sample material (a 5):
the sample material (a5) was prepared in the same manner as the sample material (a 4).
Preparation of half-cell (B5):
the procedure and conditions for preparing a half cell (B5) from the sample material (a5) as an electrode active material were the same as in example 1.
Comparative example 1
Single crystal H-Nb used in comparative example 1 2 O 5 Namely, the single crystal H-Nb prepared in example 1 2 O 5 (1 #). Directly using the obtained single crystal H-Nb 2 O 5 (1#) as a sample material (A6) of comparative example 1
The procedure and conditions for preparing a half cell (B6) from the sample material (a6) as an electrode active material were the same as in example 1.
Comparative example 2
Single crystal T-Nb 2 O 5 Preparation of (4 #):
putting the corundum crucible filled with 5g of niobium carbide into a muffle furnace, and heating to 700 ℃ at a heating rate of 2 ℃/min; keeping the temperature for heat treatment for 12h, and then reducing the temperature to room temperature at the speed of 10 ℃/min to obtain the monocrystal T-Nb 2 O 5 (4#)；
Preparation of sample material (a 7):
1g of the obtained single crystal T-Nb was weighed 2 O 5 (4#) material was uniformly dispersed in Tris buffer aqueous solution with pH 8.5 by sonication for 30 minutes, and single crystal T-Nb was continuously stirred 2 O 5 (4#) dispersion; weighing 0.36g of dopamine, dissolving the dopamine in 10mL of deionized water to prepare a dopamine solution; dropwise adding the obtained dopamine solution into the stirred single crystal T-Nb 2 O 5 (4#) the dispersion liquid is continuously stirred for 24 hours, and dopamine is subjected to polymerization reaction on the surface of the material; washing with ethanol for three times after the polymerization reaction is completed, centrifuging to obtain product, and standing at 90 deg.CDrying in an oven for 12 h; and transferring the dried product to a porcelain boat, putting the porcelain boat into a tubular furnace, heating to 700 ℃ at a speed of 5 ℃/min in an argon atmosphere, preserving the temperature for 2h, and cooling to room temperature at a speed of 5 ℃/min after the carbonization reaction is finished to obtain the composite sample material (A7).
Preparation of half-cell (B7):
the procedure and conditions for preparing a half cell (B7) from the sample material (a7) as an electrode active material were the same as in example 1.
Comparative example 3
Polycrystalline Nb 2 O 5 Preparation of (5 #):
putting the corundum crucible filled with 5g of niobium carbide into a muffle furnace, and heating to 1400 ℃ at the heating rate of 2 ℃/min; keeping the temperature for heat treatment for 12h, and then cooling to room temperature at the speed of 10 ℃/min to obtain the polycrystalline Nb 2 O 5 (5#)；
Preparation of sample material (A8):
1g of the obtained polycrystalline Nb was weighed 2 O 5 (5#) material was uniformly dispersed in Tris buffer aqueous solution with pH 8.5 by ultrasonic treatment for 30 minutes, and polycrystalline Nb was continuously stirred 2 O 5 (5#) dispersion; weighing 0.36g of dopamine, and dissolving the dopamine in 10mL of deionized water to prepare a dopamine solution; dropwise adding the obtained dopamine solution into the polycrystalline Nb in stirring 2 O 5 (5#) the dispersion liquid is continuously stirred for 24 hours, and dopamine is subjected to polymerization reaction on the surface of the material; after the polymerization reaction is finished, washing the mixture for three times by using ethanol, centrifugally separating the mixture to obtain a product, and drying the product in an oven for 12 hours at the temperature of 90 ℃; and transferring the dried product to a porcelain boat, putting the porcelain boat into a tube furnace, heating to 850 ℃ at 5 ℃/min in an argon atmosphere, preserving heat for 2h, and cooling to room temperature at 5 ℃/min after the carbonization reaction is finished to obtain a composite sample material (A8).
Preparation of half-cell (B8):
the procedure and conditions for preparing a half cell (B8) from the sample material (A8) as an electrode active material were the same as in example 1.
Comparative example 4
Polycrystalline Nb 2 O 5 Preparation of (6 #):
the corundum crucible containing 5g of niobium carbide was placed in a muffle furnace at 2 deg.CHeating to 1400 ℃ at a heating rate of/min; keeping the temperature for heat treatment for 6h, and then cooling to room temperature at the speed of 10 ℃/min to obtain the polycrystalline Nb 2 O 5 (6#)；
Preparation of sample material (a 9):
1g of the obtained polycrystalline Nb was weighed 2 O 5 (6#) material was uniformly dispersed in Tris buffer aqueous solution with pH 8.5 by ultrasonic treatment for 30 minutes, and single crystal polycrystalline Nb was continuously stirred 2 O 5 (6#) dispersion; weighing 0.36g of dopamine, and dissolving the dopamine in 10mL of deionized water to prepare a dopamine solution; dropwise adding the obtained dopamine solution into the polycrystalline Nb in stirring 2 O 5 (5#) the dispersion liquid is continuously stirred for 24 hours, and dopamine is subjected to polymerization reaction on the surface of the material; after the polymerization reaction is finished, washing the mixture for three times by using ethanol, centrifugally separating the mixture to obtain a product, and drying the product in an oven for 12 hours at the temperature of 90 ℃; and transferring the dried product to a porcelain boat, putting the porcelain boat into a tube furnace, heating to 850 ℃ at 5 ℃/min in an argon atmosphere, preserving heat for 2h, and cooling to room temperature at 5 ℃/min after the carbonization reaction is finished to obtain a composite sample material (A9).
Preparation of half-cell (B9):
the procedure and conditions for preparing a half cell (B9) from the sample material (a9) as an electrode active material were the same as in example 1.
Comparative example 5
Polycrystalline Nb 2 O 5 Preparation of (7 #):
putting the corundum crucible filled with 5g of niobium carbide into a muffle furnace, and heating to 1400 ℃ at the heating rate of 2 ℃/min; keeping the temperature for heat treatment for 48h, and then cooling to room temperature at the speed of 10 ℃/min to obtain the polycrystalline Nb 2 O 5 (7#)；
Preparation of sample material (a 10):
the sample material (a10) was prepared in the same manner as the sample material (a 9).
Preparation of half-cell (B10):
the procedure and conditions for preparing a half cell (B10) from the sample material (a10) as an electrode active material were the same as in example 1.
Example 6Nb 2 O 5 XRD structure characterization of sample (1# -7 #)
Respectively carrying out structural characterization on samples 1# to 7#, and XRD (X-ray diffraction) tests show that pure-phase micron-grade single crystal H-Nb can be obtained by calcining niobium carbide and niobium dioxide which are used as raw materials at the calcining temperature of 1000 ℃ in oxygen for 12 hours 2 O 5 (ii) a The single crystal T-Nb is obtained by taking niobium carbide as a raw material and calcining the niobium carbide for 12 hours at a temperature lower than the optional temperature (700 ℃) in oxygen 2 O 5 (ii) a The polycrystalline Nb can be obtained by calcining niobium hydroxide as a raw material at the calcining temperature of 1000 ℃ in oxygen for 12h 2 O 5 (ii) a The method is characterized in that niobium carbide is used as a raw material, the niobium carbide is calcined for 12 hours in oxygen at a temperature higher than an optional temperature (1400 ℃) or the calcination time in oxygen at a temperature of 1000 ℃ is out of an optional time range (6 hours and 48 hours), and polycrystalline Nb is obtained 2 O 5 ；
Typically represented by sample # 1, fig. 1 is the XRD pattern of sample # 1.
EXAMPLE 7 XRD Structure characterization of sample materials (A1-A10)
Respectively carrying out structural characterization on the sample materials A1-A10, and XRD (X-ray diffraction) tests show that all the sample materials A1-A10 have the crystal phases corresponding to Nb 2 O 5 The samples were identical.
Typically represented by sample a1, fig. 1 is an XRD pattern of sample a 1.
EXAMPLE 8 TEM structural characterization of sample materials (A1-A10)
Respectively carrying out structure characterization on the sample materials A1-A10, wherein TEM (transmission electron microscope) tests show that the thickness of a carbon shell of the sample material with the polymerization reaction time of 24 hours and the carbonization temperature of 850 ℃ is about 10 nm; the polymerization reaction time is 12 hours, and the thickness of the carbon shell of the sample material with the carbonization temperature of 850 ℃ is about 6 nm; the thickness of the carbon shell of the sample material with the polymerization reaction time of 48h or the carbonization temperature of 700 ℃ is about 20 nm.
Typically, sample a1 is used as a representative, and fig. 2 is a TEM image of sample a 1.
Example 9 SEM topography characterization of sample materials (A1-A5)
Respectively carrying out morphology characterization on the sample materials A1-A10, wherein SEM (scanning electron microscope) tests show that the longest direction size of the sample material particles is 2-5 mu m after the sample materials are calcined for 12 hours at the calcination temperature of 1000 ℃ in oxygen; calcining for 12 hours at a temperature lower than the optional temperature (700 ℃) in oxygen or calcining for 6 hours at a temperature of 1000 ℃ in oxygen to obtain sample material particles with the longest dimension of 2-3 mu m; the longest dimension of the sample material particles obtained by calcination in oxygen at a temperature higher than the optional temperature (1400 ℃) for 12 hours or calcination in oxygen at a temperature of 1000 ℃ for 48 hours is 6 to 10 mu m.
Typically represented by sample a1, fig. 3 is an SEM image of sample a 1.
Example 10 thermogravimetric analysis of the composite materials (A1-A3)
Performing thermogravimetric analysis on the sample materials A1-A10 by using a thermogravimetric analyzer respectively to obtain carbon content data shown in the table 1, wherein the carbon content of the sample material with the carbonization temperature of 850 ℃ is in a preferred range (2.5-3.5 wt%) after the polymerization reaction time is 24 hours; the sample material with the polymerization time of 12h and the carbonization temperature of 850 ℃ has lower carbon content (2.1 wt%); the sample material with the polymerization reaction time of 48 hours or the carbonization temperature of 700 ℃ has higher carbon content (4.2-4.5 wt%).
TABLE 1 sample materials A1-A10 carbon content
Figure BDA0002306603210000111
EXAMPLE 11 Performance testing of half cells (B1-B10)
Rate capability and cycle performance tests are respectively carried out on the half-cells B1-B10 to obtain electrochemical performance data shown in the table 2, and the electrochemical performance tests show that the carbon layer effectively improves the rate capability and the cycle stability of the sample material half-cell; single crystal H-Nb 2 O 5 Sample ratio single crystal T-Nb 2 O 5 And polycrystalline Nb 2 O 5 Higher capacity and cycle stability; single crystal H-Nb prepared by the invention 2 O 5 The composite material has proper particle size and carbon layer thickness and shows excellent electrochemical performance. Taking a half cell B1 as a representative, FIG. 4 is a charge-discharge curve of a half cell B1, FIG. 5 is a rate capability of a half cell B1, and FIG. 6 is a cycle capability of a half cell B1.
TABLE 2 Performance testing of half-cells (B1-B10)
Figure BDA0002306603210000112
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (7)

1. A lithium ion battery or a lithium ion capacitor is characterized by comprising a negative electrode material;
the anode material comprises a composite material;
the composite material is monocrystal H-Nb coated with nano carbon layer 2 O 5 The core-shell structure of (1);
wherein the core is single crystal H-Nb 2 O 5 Particles, the longest dimension of which is 2-5 μm, the shell is a nano carbon layer, and the thickness is 10-20 nm;
the preparation method of the composite material at least comprises the following steps:
a) obtaining single crystal H-Nb 2 O 5 ；
b) Will contain single crystal H-Nb 2 O 5 Reacting with a carbon source mixture, and carbonizing to obtain the nano carbon layer coated single crystal H-Nb 2 O 5 ；
The single crystal of H-Nb in step a) 2 O 5 The obtaining method comprises the following steps: the raw material containing niobium source is mixed with 2 o The temperature rises to 1000 at a temperature rise rate of C/min o C; maintaining the temperature for 12h, and then performing heat treatment at the temperature of 10 o The speed of C/min is reduced to room temperature to obtain the single crystal H-Nb 2 O 5 ；
The niobium source is niobium carbide or niobium dioxide;
the carbon source is dopamine;
step b) comprises at least the following steps:
b-1) adding a solution containing a carbon source to a solution containing single crystals of H-Nb with stirring 2 O 5 Stirring and polymerizing for 12-48H to obtain the carbon precursor coated monocrystal H-Nb 2 O 5 ；
b-2) single crystal H-Nb coating the carbon precursor 2 O 5 Carbonizing at 850 deg.C o C, obtaining the composite material;
the composite had a reversible capacity of 270 mAh/g.
2. The lithium ion battery or the lithium ion capacitor of claim 1, wherein the nanocarbon layer coats a single crystal of H-Nb 2 O 5 The content of the medium carbon is 2.0-4.0 wt%.
3. The lithium ion battery or lithium ion capacitor of claim 1, wherein the carbon source is reacted with the single crystal H-Nb in step b) 2 O 5 The mass ratio of (A) to (B) is 1: 10-1: 4.
4. The lithium ion battery or lithium ion capacitor according to claim 1,
the carbonization treatment conditions are as follows:
the reaction temperature rise rate is 1-5 o C/min; the reaction time is 2-6 h;
the carbonization is performed under an inert atmosphere.
5. The lithium ion battery or the lithium ion capacitor according to claim 1, wherein the temperature is reduced after the carbonization treatment; the cooling rate is 1-10 o C/min。
6. The lithium ion battery or lithium ion capacitor according to claim 1,
the single crystal H-Nb 2 O 5 The solid content of the dispersion is 0.05-5.0 wt%;
the single crystal of H-Nb 2 O 5 Dispersion of (2)The liquid comprises a solution buffer;
the pH value of the dispersion liquid is 8-9;
the solution buffer is at least one of Tris hydrochloride (Tris), potassium dihydrogen phosphate and sodium dihydrogen phosphate.
7. The lithium ion battery or the lithium ion capacitor according to claim 1, wherein the concentration of the solution is 0.05 to 0.5 mol/L; the solution comprises a solvent;
the solvent comprises at least one of water, methanol, ethanol, propanol and glycol.
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