CN117577844A - Niobium oxide composite energy storage material and preparation method and application thereof - Google Patents

Niobium oxide composite energy storage material and preparation method and application thereof Download PDF

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Publication number
CN117577844A
CN117577844A CN202311579359.4A CN202311579359A CN117577844A CN 117577844 A CN117577844 A CN 117577844A CN 202311579359 A CN202311579359 A CN 202311579359A CN 117577844 A CN117577844 A CN 117577844A
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energy storage
niobium
niobium oxide
storage material
composite energy
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王颖
熊梓淇
户秀琼
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Panzhihua University
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Panzhihua University
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

Abstract

The invention discloses a niobium oxide composite energy storage material, a preparation method and application thereof, and belongs to the field of electrochemical energy. The niobium oxide composite energy storage material comprises composite particles, wherein the composite particles comprise a niobium oxide matrix and a nonmetallic carbon material; the nonmetallic carbon material is dispersed and loaded on the surface of the niobium oxide matrix. The preparation method of the niobium oxide composite energy storage material comprises the steps of preparing niobium oxide, carbonizing and the like. The niobium oxide composite energy storage material disclosed by the invention is prepared in one step, is simple in method, easy to obtain, high in reproducibility, free of pollution, easy to control in product structure, and can be applied to sodium ion batteries, lithium ion batteries and lithium sulfur batteries, and has a very wide application prospect.

Description

Niobium oxide composite energy storage material and preparation method and application thereof
Technical Field
The invention belongs to the field of electrochemical energy, and particularly relates to a niobium oxide composite energy storage material, and a preparation method and application thereof.
Background
The Lithium Ion Battery (LIB) is one of the most promising energy storage power supplies with extremely high commercial application at present, and has the advantages of high specific energy, low self-discharge, good cycle performance, no memory, environmental protection and the like. However, with the progress of economic globalization and the large-scale use of irreversible fossil fuels, the problems of environmental pollution and energy shortage are increasingly prominent, the demand of the market for lithium is rapidly increased, the lithium resource reserves in the crust are relatively less, the distribution is uneven, and the problems of high lithium price and the like are caused. However, the current lithium ion battery cannot meet the requirements of high energy density and low cost of a large-scale energy storage system, and cannot meet the range (500 km/time charging) of an electric automobile and a fuel oil automobile. Therefore, it is of great importance to develop new generation energy storage systems that have high energy density, low cost, long life and are environmentally friendly.
The sodium ion battery has a lithium storage mechanism similar to that of a lithium ion battery, and the advantages of high sodium resource storage, low cost and the like make the rechargeable sodium ion battery an important supplement for lithium ions, and the rechargeable sodium ion battery is widely focused. However, sodium ion batteries also have certain problems, such as poor conductivity of the anode material, poor reaction kinetics of sodium ions and large radius of sodium ions, and the abrupt change of the buffer material volume in the deintercalation process can not ensure the structure and electrochemical stability of the buffer material, so that the buffer material can be suitable for stable deintercalation of sodium ions and less electrode materials are embedded.
The lithium-sulfur battery consists of a sulfur anode and a metal lithium cathode, has the theoretical energy density of 2600Wh/kg, is rich in natural sulfur storage, has the high theoretical specific capacity of 1675mAh/g, is low in price and is environment-friendly. Therefore, lithium sulfur batteries are considered as one of the next-generation battery candidates, and have been widely studied. Although Li-S batteries offer significant advantages, sulfur anodes still present a number of serious problems: active material S and final product lithium sulfide (Li 2 S)Are insulators and have poor electronic conductivity; s and Li 2 The S density is greatly different, so that the electrode has huge volume change (about 80 percent) in the process of charging and discharging; in particular, lithium polysulfide produced during charge and discharge has extremely high solubility in ether electrolyte, resulting in a "shuttling effect". The shuttle effect can lead to problems of low active material utilization, low coulombic efficiency, short cycle life, and the like. Therefore, the dissolution shuttle of the polysulfide intermediate is one of the key difficulties to be solved in the lithium sulfur battery at present.
Therefore, development of a battery compatible with lithium ion batteries, sodium ion batteries and lithium sulfur batteries, and capable of rapidly and stably storing energy is a current problem to be solved.
Disclosure of Invention
The invention aims to solve the technical problems of effectively improving the energy storage performance of the traditional lithium ion battery, reducing the cost, solving the problems of poor cycling stability of the sodium ion battery and effectively inhibiting the dissolution shuttle effect of the lithium sulfur battery, and providing a niobium oxide composite energy storage material and a preparation method and application thereof in order to overcome the defects and the shortcomings in the prior art.
The technical scheme adopted for solving the technical problems is as follows: the niobium oxide composite energy storage material comprises composite particles, wherein the composite particles comprise a niobium oxide matrix and a nonmetallic carbon material; the nonmetallic carbon material is dispersed and loaded on the surface of the niobium oxide matrix.
The molecular formula of the niobium oxide matrix is Nb x O y Is in a multi-layer sheet structure.
The nonmetallic carbon material is at least one of carbon nano tube, super P, graphene, glycol and glucose carbonization.
The preparation method of the niobium oxide composite energy storage material comprises the following steps:
a. directly calcining and oxidizing the niobium-containing MXene material in air or in oxygen atmosphere, and fully oxidizing to obtain niobium-containing oxide;
b. and d, uniformly mixing the non-metal carbon material with the niobium-containing oxide obtained in the step a, and fully carbonizing in a carbon dioxide atmosphere to obtain the niobium oxide composite energy storage material.
In the step a, the niobium-containing MXene material is niobium carbide (Nb) 2 CT x ) MXene, niobium aluminum carbide (Nb) 4 AlC 3 ) MAX phase ceramic material and niobium aluminum carbide (Nb) 2 AlC) MAX phase ceramic material.
In the step a, the calcination oxidation temperature is 350-1000 ℃, the time is 1-10h, and the heating rate is 1-10 ℃/min.
In the step b, the nonmetallic carbon material is at least one of carbon nanotubes, super P, graphene, ethylene glycol and glucose carbonization.
In the step b, the mass ratio of the nonmetallic carbon materials to the niobium-containing oxide is 1-10:1.
In the step b, the carbonization is carried out in a tube furnace, the carbonization temperature is 400-1000 ℃, and the carbonization time is 0.5-6h.
The niobium oxide composite energy storage material can be applied to sodium ion batteries, lithium ion batteries and lithium sulfur batteries.
The beneficial effects of the invention are as follows: the niobium oxide composite energy storage material has a multilayer layered structure, and the layered structure can effectively adsorb lithium ions to form a surface capacitance, so that the theoretical capacity is effectively improved. Is a binary transition metal sulfide, effectively improves the conductivity of the electrode material, and ensures the structure and electrochemical stability of the buffer material due to the abrupt change of the volume of the buffer material in the process of sodium ion deintercalation. The niobium oxide composite energy storage material provided by the invention provides an effective diffusion path for electrons and ions, relieves the volume expansion in the material deintercalation process, effectively inhibits the shuttle effect, and ensures the structure and electrochemical stability.
The niobium oxide composite energy storage material disclosed by the invention is prepared in one step, is simple in method, easy to obtain, high in reproducibility, free of pollution, easy to control in product structure, and can be applied to sodium ion batteries, lithium ion batteries and lithium sulfur batteries, and has a very wide application prospect.
Drawings
FIG. 1 shows a process for producing niobium carbide (Nb) in example 1 2 CT x ) SEM images of MXene material;
FIG. 2 shows niobium carbide (Nb) as provided in example 1 2 CT x ) Nb after MXene material oxidation 2 O 5 A field emission map;
FIG. 3 shows a niobium carbide (Nb) as provided in example 1 2 CT x ) Nb after MXene material oxidation 2 O 5 A field emission map;
FIG. 4 shows a niobium carbide (Nb) as provided in example 1 2 CT x ) Nb after MXene material oxidation 2 O 5 Element Mapping diagram;
FIG. 5 is a drawing of an aluminum niobium carbide (Nb) provided in example 2 4 AlC 3 ) SEM image of MAX phase ceramic material;
FIG. 6 is a drawing of an aluminum niobium carbide (Nb) provided in example 2 4 AlC 3 ) MAX phase ceramic material oxide Nb x O y SEM image;
FIG. 7 is a drawing of an aluminum niobium carbide (Nb) provided in example 3 2 AlC) SEM image of MAX phase ceramic material;
FIG. 8 is a drawing of an aluminum niobium carbide (Nb) provided in example 3 2 AlC) MAX phase ceramic material oxide Nb x O y SEM image;
FIG. 9 shows niobium carbide (Nb) as provided in example 1 2 CT x ) An MXene material thermogravimetric curve;
FIG. 10 is a drawing of an aluminum niobium carbide (Nb) provided in example 2 4 AlC 3 ) MAX phase ceramic material thermogravimetric curve;
FIG. 11 is a drawing of an aluminum niobium carbide (Nb) provided in example 3 2 AlC) MAX phase ceramic material thermogravimetric curve;
FIG. 12 shows niobium carbide (Nb) as provided in example 1 2 CT x ) Nb after MXene material oxidation 2 O 5 xrd；
FIG. 13 shows Nb provided in example 1 2 O 5 As a lithium battery cathode charge-discharge curve;
FIG. 14 is a graph of S@Nb provided in example 1 2 O 5 As a lithium sulfur positive electrode charge-discharge curve;
FIG. 15 shows Nb provided in example 1 2 O 5 As a sodium-electricity negative electrode charge-discharge curve;
FIG. 16 is a schematic illustration of the process of example 2Niobium aluminum carbide (Nb) 4 AlC 3 ) MAX phase ceramic material oxide Nb x O y As a lithium battery cathode charge-discharge curve;
FIG. 17 is a graph of S@Nb provided in example 2 x O y (Nb 4 AlC 3 Oxide) as a lithium sulfur positive electrode charge-discharge curve;
FIG. 18 is a drawing of an aluminum niobium carbide (Nb) provided in example 3 4 AlC 3 ) MAX phase ceramic material oxide Nb x O y As a lithium battery cathode charge-discharge curve;
FIG. 19 is a graph of S@Nb provided in example 3 x O y (Nb 2 AlC oxide) as a lithium sulfur positive electrode charge-discharge curve.
Detailed Description
The technical scheme of the invention can be implemented in the following way.
A niobium oxide composite energy storage material comprises composite particles, wherein the composite particles comprise a niobium oxide matrix and a nonmetallic carbon material; the nonmetallic carbon material is dispersedly loaded on the surface of the niobium oxide.
Preferably, the niobium oxide matrix has the formula Nb x O y And has a multi-layer lamellar structure.
Under normal conditions, the traditional lithium ion battery has low energy density, high cost, poor cycling stability of the sodium ion battery and serious dissolution shuttle effect of the lithium sulfur battery. The niobium oxide composite energy storage material has a multilayer layered structure, and the layered structure can effectively adsorb lithium ions to form a surface capacitance, so that the theoretical capacity is effectively improved. And the layered structure provides an effective diffusion path for electrons and ions, relieves volume expansion in the material deintercalation process, effectively inhibits the shuttle effect, and ensures the structure and electrochemical stability.
Preferably, the nonmetallic carbon material is at least one of carbon nanotubes, superP, graphene, ethylene glycol and glucose carbonization.
As a general technical concept, the present invention also provides a method for preparing the niobium oxide composite energy storage material as described above, characterized in that the method comprises the steps of:
step (1): oxidizing the niobium-containing MXene material, and synthesizing niobium oxide through oxidation;
step (2): adding a proper amount of non-metallic carbon material into the niobium oxide, stirring and mixing uniformly, and fully carbonizing in a tube furnace under the carbon dioxide atmosphere to obtain the niobium oxide composite energy storage material.
Preferably, the method for oxidizing and synthesizing in the step (1) is as follows: and directly oxidizing the niobium-containing MXene material in air or in an oxygen atmosphere, and fully oxidizing to obtain the niobium-containing oxide.
Preferably, the niobium-containing MXene material is niobium carbide (Nb) 2 CT x ) MXene or niobium aluminum carbide (Nb) 4 AlC 3 ) MAX phase ceramic material or niobium aluminium carbide (Nb) 2 AlC) MAX phase ceramic material, the calcining temperature is 350-1000 ℃, the calcining time is 1-10 hours, and the heating rate is 1-10 ℃/min.
Preferably, the carbon material in the step (2) is at least one of carbon nanotubes, super P, graphene, ethylene glycol and glucose carbonization; the carbonization temperature is 400-1000 ℃, the carbonization time is 0.5-6h, and the carbonization gas is carbon dioxide.
Preferably, the mass ratio of the nonmetallic carbon material to the niobium oxide is 1-10:1.
Preferably, the mixing and stirring time of the nonmetallic carbon materials and the niobium oxide is 1-24h.
Preferably, the invention also provides a sodium ion battery, a lithium ion battery and a lithium sulfur battery, which comprise the niobium oxide composite energy storage material.
The technical scheme and effect of the present invention will be further described by practical examples.
Examples
Example 1
1. Preparation of niobium oxide composite energy storage material
The product of the embodiment is the niobium oxide composite energy storage material, and the non-metallic carbon material is carbonized by ethylene glycol at high temperature.
The niobium oxide composite energy storage material is prepared according to the following method:
(1) Synthesis of niobium oxide: niobium carbide (Nb) 2 CT x ) The MXene material was subjected to thermogravimetric testing and the oxidation temperature was determined from the thermogravimetric curve. Niobium carbide (Nb) 2 CT x ) Placing the MXene material in a tube furnace, heating up to 750 ℃ at a speed of 2 ℃/min, and keeping for 4 hours to oxidize and synthesize niobium oxide;
FIG. 1 shows a niobium carbide (Nb) 2 CT x ) SEM image of MXene material, FIGS. 2 and 3 show niobium carbide (Nb) 2 CT x ) Niobium oxide (Nb) after oxidation of MXene material 2 O 5 ) The field emission diagram shows that the synthesized oxide has a multi-layer lamellar structure, good appearance, unchanged appearance after high-temperature oxidation, and stable structure. FIG. 9 shows niobium carbide (Nb) 2 CT x ) The thermal weight curve of the MXene material is smooth after oxidation to 750 ℃, and the weight of the material is not increased continuously; FIG. 12 shows niobium carbide (Nb) 2 CT x ) mXene material oxide xrd ， From the figure, diffraction peaks and Nb can be seen 2 O 5 And NbAlO 4 The diffraction peaks correspond to the formation of NbAlO4 due to the synthesis of niobium carbide (Nb 2 CT x ) It is difficult to completely remove the Al element by etching with hydrofluoric acid when the MXene material is used. FIG. 4 shows niobium carbide (Nb) 2 CT x ) Nb after MXene material oxidation 2 O 5 The element Mapping graph shows that the synthetic oxide contains Nb, O and a small amount of Al elements.
(2) Adding a proper amount of ethylene glycol into the niobium oxide (the mass ratio of the ethylene glycol to the niobium oxide is 10:1), stirring and mixing uniformly for 3 hours, placing the mixture into a tube furnace, and carbonizing at 800 ℃ for 2 hours in a carbon dioxide atmosphere to obtain the niobium oxide composite energy storage material.
2. Performance detection
(1) Assembling a lithium ion battery: nb prepared in the example 2 O 5 The composite energy storage material is used as an active substance, PVDF is used as a binder, a conductive agent (SuperP and carbon nano tubes) is added, then stirring pulping is carried out, the mixture is coated on a copper foil, and finally, a negative plate is obtained through baking and grinding, wherein the active substance is: conductive agent: binder=75:10:5:10.A lithium ion battery was assembled using a solution of a metal lithium sheet as a counter electrode, celgard2400 separator (Celgard Co., USA), ethylene Carbonate (EC) +dimethyl carbonate (DMC) +diethyl carbonate (DEC) (VEC: VDMC: VDEC=1:1:1) of 1M LiPF6 as an electrolyte, and a simulated battery was assembled in an argon-filled glove box.
The test method for testing the electrochemical performance comprises the following steps:
1. the surface morphology, particle size, etc. of the sample were observed using a Hitachi S4800 scanning electron microscope.
2. And (3) testing the buckling charge and discharge performance: fig. 13 shows Nb provided in this embodiment 2 O 5 And a 25-turn charge-discharge curve of the composite anode material. The graph shows that the first-circle discharge specific capacity of the composite material is 478.258mAh/g, the 25-circle charge specific capacity is 191.866mAh/g, the discharge specific capacity is 191.874mAh/g, and the charge-discharge multiplying power after 25 circles of circulation is 99.996%.
(2) Assembling a sodium ion battery: nb prepared in the example 2 O 5 The composite energy storage material is used as an active substance, PVDF is used as a binder, a conductive agent (SuperP and carbon nano tubes) is added, then stirring pulping is carried out, the mixture is coated on a copper foil, and finally, a negative plate is obtained through baking and grinding, wherein the active substance is: conductive agent: binder=75:10:5:10. A sodium ion battery was assembled using a metallic lithium sheet as a counter electrode, celgard2400 separator (Celgard Co., USA), a 1mol/L solution of NaPF6 in Ethylene Carbonate (EC) +diethyl carbonate (DEC) (VEC: VDEC=1:1) as an electrolyte, and a simulated battery was assembled in an argon-filled glove box.
The test method for testing the electrochemical performance comprises the following steps:
1. the surface morphology, particle size, etc. of the sample were observed using a Hitachi S4800 scanning electron microscope.
2. And (3) testing the buckling charge and discharge performance: fig. 15 shows Nb provided in this embodiment 2 O 5 And 3 circles of charge-discharge curves of the composite anode material. From the graph, the first-turn charge specific capacity of the composite material is 79.3mAh/g, and the discharge specific capacity of the composite material is 82.8mAh/g.
(3) Assembling a lithium-sulfur battery: nb prepared in the example 2 O 5 The composite energy storage material is compounded with S according to the ratio of 7:3,S@Nb 2 O 5 as an active substance, PVDF is used as a binder, a conductive agent (Super P) is added, then the mixture is stirred, pulped and coated on a carbon foil, and finally, the positive plate is prepared through baking and grinding, and the active substance is prepared: conductive agent: binder=7:2:1. A metal lithium sheet is used as a counter electrode, celgard2400 diaphragm (Celgard company of U.S.) is used as a mixed solution of ethylene glycol dimethyl ether (DME) and Dioxolane (DOL) (volume ratio 1:1) of 1M lithium bis (trifluoromethanesulfonyl imide) (LiTFSI), and LiNO is contained 3 LiNO in electrolyte of additive 3 The concentration was 2%, and a simulated lithium sulfur battery was assembled in an argon-filled glove box.
The test method for testing the electrochemical performance comprises the following steps:
1. the surface morphology, particle size, etc. of the sample were observed using a Hitachi S4800 scanning electron microscope.
2. And (3) testing the buckling charge and discharge performance: fig. 14 shows Nb provided in this embodiment 2 O 5 And a 25-turn charge-discharge curve of the composite anode material. The graph shows that the first-circle charging specific capacity 775.078mAh/g, the discharging specific capacity 803.991mAh/g, the 25-circle charging specific capacity 595.039mAh/g, the discharging specific capacity 593.072mAh/g and the charging and discharging multiplying power after 25 circles of circulation are still close to 100%.
Example 2
1. Preparation of niobium oxide composite energy storage material
The product of the embodiment is the niobium oxide composite energy storage material, and the non-metallic carbon material is carbonized by ethylene glycol at high temperature.
The niobium oxide composite energy storage material is prepared according to the following method:
(1) Synthesis of niobium oxide: niobium aluminum carbide (Nb) 4 AlC 3 ) And carrying out thermal gravimetric test on the MAX phase ceramic material, and determining the oxidation temperature according to a thermal gravimetric curve. Under oxygen atmosphere, niobium aluminum carbide (Nb 4 AlC 3 ) Placing the MAX phase ceramic material in a tube furnace, heating up to 750 ℃ according to the speed of 1 ℃/min, and keeping for 2 hours to oxidize and synthesize niobium oxide;
FIG. 5 shows a sample of the niobium aluminum carbide (Nb) 4 AlC 3 ) SEM image of MAX phase ceramic material, FIG. 6 showsNiobium aluminum carbide (Nb) 4 AlC 3 ) SEM image of niobium oxide after oxidation of MAX phase ceramic material shows that the synthesized oxide is multilayer lamellar structure, good appearance, unchanged appearance after high temperature oxidation, and stable structure. FIG. 10 is a drawing of niobium aluminum carbide (Nb 4 AlC 3 ) The curve of the thermal weight of the MAX phase ceramic material is smooth after oxidation to 750 ℃ as can be seen from the graph, and the weight of the material does not increase continuously.
(2) Adding a proper amount of ethylene glycol into the niobium oxide (the mass ratio of the ethylene glycol to the niobium oxide is 8:1), stirring and mixing uniformly for 2 hours, placing the mixture into a tube furnace, and carbonizing at 700 ℃ for 2 hours in a carbon dioxide atmosphere to obtain the niobium oxide composite energy storage material.
2. Performance detection
(1) Assembling a lithium ion battery: nb prepared in the example x O y The procedure of example 1 was followed except that the composite energy storage material was used as the active material. The charge and discharge performance test was conducted in the same manner as in example 1, and the results were shown in FIG. 16, which shows that the aluminum carbide (Nb) 4 AlC 3 ) MAX phase ceramic material oxide Nb x O y The lithium battery cathode is shown as a charge-discharge curve.
(2) Assembling a lithium-sulfur battery: nb prepared in the example x O y Composite energy storage material and S are compounded according to the ratio of 7:3, and S@Nb 2 O 5 The remaining procedure was as in example 1, as active substance. The procedure of the charge and discharge performance test is the same as that of example 1, and the result is shown in a graph 17S@Nb x O y (Nb 4 AlC 3 Oxide) is shown as a charge-discharge curve of a lithium sulfur positive electrode.
Example 3
1. Preparation of niobium oxide composite energy storage material
The product of the embodiment is the niobium oxide composite energy storage material, and the non-metallic carbon material is carbonized by ethylene glycol at high temperature.
The niobium oxide composite energy storage material is prepared according to the following method:
(1) Synthesis of niobium oxide: niobium aluminum carbide (Nb) 2 AlC) MAX phase ceramic material is subjected to thermal re-bending test according to thermal re-bendingThe line determines the oxidation temperature. Under oxygen atmosphere, niobium aluminum carbide (Nb 2 AlC) MAX phase ceramic material is placed in a tube furnace, and is heated up to 750 ℃ according to the speed of 5 ℃/min (minutes), and is oxidized and synthesized into niobium oxide for 1 hour;
FIG. 7 shows a sample of the niobium aluminum carbide (Nb) 2 AlC) MAX phase ceramic material SEM image, FIG. 8 shows niobium aluminum carbide (Nb) 2 AlC) and the SEM image of the niobium oxide after the oxidation of the MAX phase ceramic material, the image can show that the synthesized oxide is of a multi-layer laminated structure, the appearance is better, the appearance is unchanged before and after the high-temperature oxidation, and the structure is more stable. FIG. 11 is a drawing of niobium aluminum carbide (Nb 2 AlC) MAX phase ceramic material thermal weight curve, the curve is gentle after oxidation to 750 ℃ and the weight of the material is not increased continuously.
(2) Adding a proper amount of ethylene glycol into the niobium oxide (the mass ratio of the ethylene glycol to the niobium oxide is 6:1), stirring and mixing uniformly for 1h, placing the mixture into a tube furnace, and carbonizing at 600 ℃ for 1h in a carbon dioxide atmosphere to obtain the niobium oxide composite energy storage material.
2. Performance detection
(1) Assembling a lithium ion battery: nb prepared in the example x O y The procedure of example 1 was followed except that the composite energy storage material was used as the active material. The charge and discharge performance test was conducted in the same manner as in example 1, and the results were shown in FIG. 18, which shows that the aluminum carbide (Nb) 4 AlC 3 ) MAX phase ceramic material oxide Nb x O y The lithium battery cathode is shown as a charge-discharge curve.
(2) Assembling a lithium-sulfur battery: nb prepared in the example x O y Composite energy storage material and S are compounded according to the ratio of 7:3, and S@Nb 2 O 5 The remaining procedure was as in example 1, as active substance. The procedure of example 1 was followed to obtain the results shown in FIG. 19S@Nb x O y (Nb 4 AlC oxide) is shown as a lithium sulfur positive electrode charge-discharge curve.

Claims (10)

1. The niobium oxide composite energy storage material is characterized in that: comprises composite particles, wherein the composite particles comprise a niobium oxide matrix and a nonmetallic carbon material; the nonmetallic carbon material is dispersed and loaded on the surface of the niobium oxide matrix.
2. The niobium oxide composite energy storage material of claim 1, wherein: the molecular formula of the niobium oxide matrix is Nb x O y Is in a multi-layer sheet structure.
3. The niobium oxide composite energy storage material of claim 1, wherein: the nonmetallic carbon material is at least one of carbon nano tube, super P, graphene, glycol and glucose carbonization.
4. A method for preparing a niobium oxide composite energy storage material as claimed in any one of claims 1 to 3, comprising the steps of:
a. directly calcining and oxidizing the niobium-containing MXene material in air or in oxygen atmosphere, and fully oxidizing to obtain niobium-containing oxide;
b. and d, uniformly mixing the non-metal carbon material with the niobium-containing oxide obtained in the step a, and fully carbonizing in a carbon dioxide atmosphere to obtain the niobium oxide composite energy storage material.
5. The method for preparing a niobium oxide composite energy storage material as claimed in claim 4, wherein: in the step a, the niobium-containing MXene material is niobium carbide (Nb) 2 CT x ) MXene, niobium aluminum carbide (Nb) 4 AlC 3 ) MAX phase ceramic material and niobium aluminum carbide (Nb) 2 AlC) MAX phase ceramic material.
6. The method for preparing a niobium oxide composite energy storage material as claimed in claim 4, wherein: in the step a, the calcination oxidation temperature is 350-1000 ℃, the time is 1-10h, and the heating rate is 1-10 ℃/min.
7. The method for preparing a niobium oxide composite energy storage material as claimed in claim 4, wherein: in the step b, the nonmetallic carbon material is at least one of carbon nano tube, super P, graphene, ethylene glycol and glucose carbonization.
8. The method for preparing a niobium oxide composite energy storage material as claimed in claim 4, wherein: in the step b, the mass ratio of the nonmetallic carbon materials to the niobium-containing oxide is 1-10:1.
9. The method for preparing a niobium oxide composite energy storage material as claimed in claim 4, wherein: in the step b, the carbonization is carried out in a tube furnace, the carbonization temperature is 400-1000 ℃, and the carbonization time is 0.5-6h.
10. The application of the niobium oxide composite energy storage material is characterized in that: sodium ion batteries, lithium ion batteries and lithium sulfur batteries comprising the niobium oxide composite energy storage material according to any one of claims 1 to 3 and a niobium oxide composite energy storage material prepared by the method for preparing a niobium oxide composite energy storage material according to any one of claims 4 to 9.
CN202311579359.4A 2023-11-24 2023-11-24 Niobium oxide composite energy storage material and preparation method and application thereof Pending CN117577844A (en)

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