CN113666420A - Bimetal niobium oxide and carbon composite material thereof, preparation method and application - Google Patents
Bimetal niobium oxide and carbon composite material thereof, preparation method and application Download PDFInfo
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Abstract
The invention discloses a bimetal niobium oxide and a carbon composite material thereof, a preparation method and application, wherein the method comprises the following steps: (1) adding niobium-based MXene material serving as a niobium source and another alcohol solution containing a metal source into an alcohol solution of urea to obtain a precursor solution for later use; the metal source is selected from any one of Co, Mn, Mg and Sn elements. (2) And carrying out solvothermal reaction on the precursor solution, separating a solid product in the reaction solution, washing and drying to obtain the precursor. (3) Calcining the precursor in air to obtain a bimetal niobium oxide; or calcining the precursor under the oxygen-isolating condition to obtain the bimetal niobium oxide composite carbon material. The material prepared by the invention has high specific capacity when being used as a battery cathode material, has a stable crystal structure, and can effectively avoid the problems of capacity rapid attenuation and the like caused by structure collapse.
Description
Technical Field
The invention relates to the technical field of battery material preparation, in particular to a bimetal niobium oxide and a preparation method and application thereof.
Background
The information in this background section is disclosed to enhance understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms part of the prior art already known to a person of ordinary skill in the art.
Since the birth of the last century, the lithium ion battery becomes the most mature technology and the most widely applied high-energy battery system through the efforts of countless scientists. The lithium ion battery has the advantages of high energy density, high working voltage, long cycle life, no memory and the like, and is widely applied to the fields of 3C products (computer products, communication products and consumer electronics products) and electric automobiles. At present, the commercial lithium ion battery is made of a graphite negative electrode material, but the graphite material has the problems of low specific capacity, poor structural stability, excessively low charge and discharge platform and the like, and is not an ideal negative electrode material. Among various lithium ion battery cathode materials researched at present, niobium-based oxides are concerned by vast researchers by virtue of the advantages of high reversible capacity, extremely small volume expansion (3-5%), high working voltage and the like. However, the conventional niobium-based oxide negative electrode material has a low specific capacity, and has a problem of rapid capacity attenuation caused by structural collapse under a large current, which seriously hinders practical application thereof.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a bimetal niobium oxide and a preparation method and application thereof. When the material is used as a battery cathode material, the material has high specific capacity and a stable crystal structure, and can effectively avoid the problems of capacity rapid attenuation and the like caused by structure collapse. In order to achieve the purpose, the invention discloses the following technical scheme:
in a first aspect of the present invention, there is provided a bimetallic niobium oxide having an accordion-like lamellar structure of MXene material, wherein the lamellar component of the structure is a bimetallic oxide MNb having a niobite structure2O6Wherein: the MNb2O6M in (3) is selected from any one of Mn, Co, Mg and Sn elements.
In a second aspect of the present invention, there is provided a bimetallic niobium oxide composite carbon material having a structure of a sheet structure of an MXene material in an accordion shape, the sheet structure including a bimetallic oxide MNb2O6And amorphous carbon. Wherein: the MNb2O6M in (1) is selected from any one of Mn, Co, Mg and Sn, and the MNb2O6Is of a niobite structure.
In a third aspect of the present invention, there is provided a method for preparing a bi-metallic niobium oxide, comprising the steps of:
(1) adding niobium-based MXene material serving as a niobium source and another alcohol solution containing a metal source into an alcohol solution of urea to obtain a precursor solution for later use; the metal source is selected from any one of Co, Mn, Mg and Sn elements.
(2) And carrying out solvothermal reaction on the precursor solution, separating a solid product in the reaction solution, washing and drying to obtain a precursor for later use.
(3) And calcining the precursor in the air to obtain the catalyst.
In a fourth aspect of the present invention, there is provided a method for producing a bimetallic niobium oxide composite carbon material, comprising the steps of:
(i) adding niobium-based MXene material serving as a niobium source and another alcohol solution containing a metal source into an alcohol solution of urea to obtain a precursor solution for later use; the metal source is selected from any one of Co, Mn, Mg and Sn elements.
(ii) And carrying out solvothermal reaction on the precursor solution, separating a solid product in the reaction solution, washing and drying to obtain a precursor for later use.
(iii) And calcining the precursor under an oxygen-isolating condition to obtain the catalyst.
Further, in steps (1) and (i), the niobium source has the formula Nb2CTxWherein T is a surface group, typically including: -OH, -O, -F, -Cl, etc.
Further, in steps (1) and (i), the metal source is selected from water-soluble salts of Co, Mn, Mg or Sn elements; such as at least one of hydrochloride, sulfate, nitrate, acetate, and the like.
Further, in the steps (1) and (i), the alcohol solution of urea is prepared by mixing urea and ethanol according to the ratio of 1-2 g: the mixed solution formed by the ratio of 40mL has better dispersibility of the niobium-based MXene material in the ethanol solution.
Further, in the steps (1) and (i), the molar ratio of the niobium element and the metal element provided by the niobium source and the metal source in the precursor solution is 2: 1. It is to be noted that, in the present invention, since the double metal oxide MNb to be produced2O6It must be a pure phase, not a mixture of niobium oxide and metal oxide, and therefore the ratio between the niobium element (Nb) and the metal element (M) should be in accordance with MNb2O6The atomic number ratios are set to ensure that a pure phase is obtained, not a mixture.
Optionally, the total concentration of the niobium source and the metal source in the precursor solution is 0.02-0.06 mol/L.
Further, in the steps (2) and (ii), the temperature of the solvothermal reaction is preferably controlled to be 150-180 ℃, and the reaction time is preferably controlled to be 12-18 h. Through the solvothermal reaction, more active sites on the surface of the niobium-based MXene can be exposed and combined with another metal element in the solution. Moreover, since ethanol has a weak reducing property, Nb is not converted into Nb2CTxThe carbon in the catalyst is oxidized to be retained,and converted to amorphous carbon at high temperatures.
Further, in the steps (2) and (ii), solid products in the reaction liquid are separated through filtration, centrifugation and other modes, then the solid products are sequentially washed by ethanol and deionized water, and then the solid products are dried for 10-24 hours at the temperature of 50-80 ℃ to obtain the precursor.
Further, in the steps (3) and (iii), the calcination temperature is preferably controlled to be 700-900 ℃, and the calcination time is preferably controlled to be 4-6 hours. It should be noted that the calcination temperature and time may have an influence on the phase of the product, for example, if the temperature is too low, a mixture of the oxide of each of the bimetallic elements and other heterogeneous phases may be generated.
Further, in the step (ii), the oxygen-isolating condition provides an oxygen-isolating reaction environment by using inert gas or nitrogen as shielding gas so as to retain the carbon in the precursor, and obtain the MNb containing carbon2O6A composite material.
In a fourth aspect of the present invention, an application of the bi-metal niobium oxide composite carbon material in an energy storage component is provided, and the bi-metal niobium oxide composite carbon material is preferably used as a negative electrode material of a lithium battery, which can improve the electrical conductivity of the negative electrode material and greatly improve the specific capacity of the battery.
Compared with the prior art, the invention has the following beneficial and unique effects:
(1) the bimetal niobium oxide and the carbon composite material thereof retain the unique structural advantages of MXene, can provide a stable framework structure, can provide a lithium ion fast de-intercalation channel to realize the fast migration of lithium ions, and are favorable for avoiding the problems of capacity fast attenuation and the like caused by structure collapse. In addition, the niobite structure of the bi-metallic niobium oxide is composed of blocks composed of shared octahedra of corners and edges. The edge sharing between the octahedrons greatly stabilizes the structure during charge/discharge. In addition, because the other metal element in the bimetal niobium oxide is different, the octahedral arrangement has certain difference, so that the niobium-based oxides with different components have certain difference, but all belong to a plane layered structure consisting of octahedrons. The niobite structure provides a wide channel for diffusion of lithium ions, thermodynamic stability of the material is improved, and the niobite structure is favorable for maintaining structural stability of the material in a lithium desorption process, so that the material has good cycle performance.
(2) In the bimetal niobium oxide and the carbon composite material thereof prepared by the invention, the synergistic effect of the bimetal elements effectively improves the conductivity of the material and greatly improves the specific capacity of the battery, and the reasons are that: for Mn, Co and Sn, the Mn, Co and Sn exist in a +2 valence state in the bimetal niobium oxide, and the outer layer exists in a lone electron or lone electron pair, so that the conductivity of the material is improved, and the electrochemical performance of the material is further improved. Tests prove that Mn, Co, Mg and Sn can achieve the purposes and can successfully synthesize the pure-phase bimetal niobium oxide.
(3) In the bimetal niobium oxide and the carbon composite material thereof prepared by the invention, additional metal elements are introduced, the atomic radii of Mg, Mn, Co and Sn are smaller than those of Nb atoms, and lithium ions are preferentially selected from NbO6Octahedrons are embedded along tunnels with larger dimensions, and smaller element units can play an important role as anchor points in relieving volume change in the circulation process, which is more beneficial to the structural stability in the continuous charge and discharge process.
(4) The de-intercalation lithium potential of the traditional niobium-based oxide and lithium titanate material is generally 1.2-1.6V (vs Li)+/Li), the high de-intercalation potential, while avoiding the formation of lithium dendrites and improving safety, limits the output of high voltage when applied in conjunction with positive electrode materials. The lithium-releasing potential of the bimetal niobium oxide and the carbon composite material thereof is mostly 0.5V (vs Li)+/Li), the potential can not only avoid the safety problem caused by the generation of lithium dendrite, but also can be well matched with the anode to output higher voltage and energy density.
(5) The niobium-based oxide serving as a negative electrode material of the lithium ion battery has the characteristics of high specific capacity, good rate capability and the like, but poor conductivity is also an inherent defect. In the invention, the carbon in the niobium-based MXene is reserved through simple solvothermal and subsequent annealing treatment, and an additional carbon coating process is not needed, so that the carbon exists in the material as amorphous carbon in the subsequent treatment. The amorphous carbon has excellent conductivity, can obviously improve the defect of poor conductivity of the oxide electrode material, and is further beneficial to the electrochemical performance of the oxide electrode material.
In conclusion, due to the synergistic effect between different metals in the bimetal oxide and the stability of the niobite structure, the bimetal niobium oxide and the carbon composite material thereof have excellent high reversible capacity and excellent cycling stability when used as the negative electrode material of the lithium battery.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows a multilayer niobium-based MXene (m-Nb) prepared in the first example2CTx) XRD spectrum (a) and SEM image (b) of (a).
FIG. 2 shows MnNb prepared in a second embodiment2O6XRD pattern (a) and SEM image (b) of @ C.
FIG. 3 shows SnNb prepared in the third embodiment2O6XRD pattern (a) and SEM image (b) of @ C.
FIG. 4 is a MgNb prepared in a fourth example2O6XRD pattern (a) and SEM image (b) of @ C.
FIG. 5 shows CoNb prepared in the fifth example2O6XRD pattern (a) and SEM image (b) of @ C.
Fig. 6 is an XRD pattern (a) and an SEM image (b) of the niobium-oxygen mixture prepared in the first comparative example.
Fig. 7 is an XRD pattern (a) and an SEM image (b) of a manganese niobium oxygen mixture prepared in a second comparative example.
FIG. 8 is a MgNb prepared by the fourth example2O6Electrochemical performance diagram (Current Density 1A g) as negative electrode material of lithium ion Battery-1）。
FIG. 9 is a comparison graph of the cycle performance of lithium ion button half cells fabricated by using the negative electrode materials prepared in the fourth and fifth embodiments and the first and second comparative examples (current density 100 mAg)-1）。
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred methods and materials described in this invention are exemplary only. The invention will now be further described with reference to the drawings and specific examples in the specification.
First embodiment
Multilayer niobium-based MXene (m-Nb)2CTx) The preparation method comprises the following steps:
(1) 10mL of deionized water was mixed with 30mL of 12M HCl, magnetically stirred for 30min to form a homogeneous hydrochloric acid solution, to which 3g of lithium fluoride (LiF) and 2g of Nb were added2And completely dissolving AlC by magnetic stirring for 30min to obtain a mixed solution.
(2) Putting the mixed solution obtained in the step (1) into a Taylor reaction kettle, and carrying out hydrothermal reaction for 48 hours at 180 ℃ so as to facilitate Nb2And etching the AlC.
(3) And (3) centrifuging the etched mixed solution obtained in the step (2), and adding the separated solid product into deionized water for repeated cleaning until the pH value of the supernatant reaches more than 6. Pouring off the supernatantAnd taking the lower layer precipitate for drying to obtain the multilayer niobium-based MXene: m-Nb2CTxAnd then standby. Further, the m-Nb2CTxThe commercially available product can also be used as it is.
Second embodiment
A preparation method of the bimetal niobium oxide comprises the following steps:
(1) 1.0g of urea was added to 40mL of absolute ethanol, and magnetically stirred until urea was completely dissolved, to obtain an alcoholic solution of urea.
(2) 0.0004mol of m-Nb prepared in the first example is taken2CTxAnd 0.0004mol of MnCl2•4H2Adding the O solid into the urea alcohol solution prepared in the step (1), firstly stirring for 1h by using a magnetic stirrer, and then carrying out ultrasonic treatment for 30min to ensure that the m-Nb is formed2CTxAnd MnCl2•4H2And completely dissolving the O to obtain a precursor solution.
(3) And (3) placing the precursor solution obtained in the step (2) in a Taylor reaction kettle for solvothermal reaction at the temperature of 160 ℃ for 18h, and placing the obtained reaction solution in a centrifuge for centrifugal separation to obtain a solid product.
(4) And (3) washing the solid product with deionized water and ethanol for several times in sequence, and then drying in an oven at 50 ℃ for 10h to obtain a precursor for later use.
(5) Placing the precursor in a tubular furnace, calcining the precursor in a nitrogen atmosphere at 900 ℃ for 5 hours at a heating rate of 5 ℃/min, and naturally cooling to room temperature after the calcination is finished to obtain the bimetal niobium oxide composite carbon material: MnNb2O6@C。
Third embodiment
A preparation method of the bimetal niobium oxide comprises the following steps:
(1) 1.5g of urea was added to 40mL of absolute ethanol, and magnetically stirred until the urea was completely dissolved, to obtain an alcoholic solution of urea.
(2) 0.0012mol of m-Nb prepared in the first example is taken2CTxAnd 0.0012mol of SnCl2Adding the solid into the urea alcohol solution prepared in the step (1), firstly stirring for 1h by using a magnetic stirrer, and then carrying out ultrasonic treatment for 30min to ensure that the m-Nb is dissolved in the solution2CTxAnd SnCl2And completely dissolving to obtain a precursor solution.
(3) And (3) placing the precursor solution obtained in the step (2) in a Taylor reaction kettle for solvothermal reaction at the temperature of 180 ℃ for 12 hours, and placing the obtained reaction solution in a centrifuge for centrifugal separation to obtain a solid product after the reaction is finished.
(4) And (3) washing the solid product with deionized water and ethanol for several times in sequence, and drying in an oven at 80 ℃ for 10h to obtain a precursor for later use.
(5) Placing the precursor in a tubular furnace, calcining the precursor in a nitrogen atmosphere at 700 ℃ for 4 hours at a heating rate of 4 ℃/min, and naturally cooling the precursor to room temperature after the calcination is finished to obtain the bimetal niobium oxide composite carbon material: SnNb2O6@C。
Fourth embodiment
A preparation method of the bimetal niobium oxide comprises the following steps:
(1) 2.0g of urea was added to 40mL of absolute ethanol and stirred magnetically until the urea was completely dissolved to give an alcoholic solution of urea.
(2) 0.0004mol of m-Nb prepared in the first example is taken2CTxAnd 0.0004mol of MgCl2Adding the solid into the urea alcohol solution prepared in the step (1), firstly stirring for 1h by using a magnetic stirrer, and then carrying out ultrasonic treatment for 30min to ensure that the m-Nb is dissolved in the solution2CTxAnd MgCl2And completely dissolving to obtain a precursor solution.
(3) And (3) placing the precursor solution obtained in the step (2) in a Taylor reaction kettle for solvothermal reaction at the temperature of 180 ℃ for 16h, and placing the obtained reaction solution in a centrifuge for centrifugal separation to obtain a solid product.
(4) And (3) washing the solid product with deionized water and ethanol for several times in sequence, and drying in an oven at 80 ℃ for 16h to obtain a precursor for later use.
(5) Placing the precursor in a tubular furnace, calcining the precursor in a nitrogen atmosphere at 800 ℃ for 5 hours at a heating rate of 5 ℃/min, and naturally cooling to room temperature after the calcination is finished to obtain the bimetal niobium oxide composite carbon material: MgNb2O6@C。
Fifth embodiment
A preparation method of the bimetal niobium oxide comprises the following steps:
(1) 1.5g of urea was added to 40mL of absolute ethanol, and magnetically stirred until the urea was completely dissolved, to obtain an alcoholic solution of urea.
(2) 0.0008mol of m-Nb prepared in the first example is taken2CTxAnd 0.0008mol of CoCl2Adding the solid into the urea alcohol solution prepared in the step (1), firstly stirring for 1h by using a magnetic stirrer, and then carrying out ultrasonic treatment for 30min to ensure that the m-Nb is dissolved in the solution2CTxAnd CoCl2And completely dissolving to obtain a precursor solution.
(3) And (3) placing the precursor solution obtained in the step (2) in a Taylor reaction kettle for solvothermal reaction at the temperature of 150 ℃ for 16h, and placing the obtained reaction solution in a centrifuge for centrifugal separation to obtain a solid product.
(4) And (3) washing the solid product with deionized water and ethanol for several times in sequence, and drying in an oven at 50 ℃ for 24h to obtain a precursor for later use.
(5) Placing the precursor in a tubular furnace, calcining the precursor in a nitrogen atmosphere at 700 ℃ for 6 hours at a heating rate of 3 ℃/min, and naturally cooling to room temperature after the calcination is finished to obtain the bimetal niobium oxide composite carbon material: CoNb2O6@C。
First comparative example
A preparation method of the bimetal niobium oxide comprises the following steps:
(1) 1.5g of urea was added to 40mL of absolute ethanol, and magnetically stirred until the urea was completely dissolved, to obtain an alcoholic solution of urea.
(2) 0.0004mol of m-Nb prepared in the first example is taken2CTxAdding the mixture into the urea alcohol solution prepared in the step (1), firstly stirring for 1 hour by using a magnetic stirrer, and then carrying out ultrasonic treatment for 30min to ensure that the m-Nb is added2CTxAnd completely dissolving to obtain a precursor solution.
(3) And (3) placing the precursor solution obtained in the step (2) in a Taylor reaction kettle for solvothermal reaction at the temperature of 180 ℃ for 16h, and placing the obtained reaction solution in a centrifuge for centrifugal separation to obtain a solid product.
(4) And (3) washing the solid product with deionized water and ethanol for several times in sequence, and drying in an oven at 80 ℃ for 16h to obtain a precursor for later use.
(5) Placing the precursor in a tube furnace, calcining the precursor in a nitrogen atmosphere at 800 ℃ for 5 hours at a heating rate of 5 ℃/min, and naturally cooling the precursor to room temperature after the calcination is finished to obtain the catalyst
Second comparative example
A preparation method of the bimetal niobium oxide comprises the following steps:
(1) 1.5g of urea was added to 40mL of absolute ethanol, and magnetically stirred until the urea was completely dissolved, to obtain an alcoholic solution of urea.
(2) 0.0012mol of m-Nb prepared in the first example is taken2CTxAnd 0.0012mol of MnCl2•4H2Adding the O solid into the urea alcohol solution prepared in the step (1), firstly stirring for 1h by using a magnetic stirrer, and then carrying out ultrasonic treatment for 30min to ensure that the m-Nb is formed2CTxAnd MnCl2•4H2And completely dissolving the O to obtain a precursor solution.
(3) And (3) placing the precursor solution obtained in the step (2) in a Taylor reaction kettle for solvothermal reaction at the temperature of 180 ℃ for 14h, and placing the obtained reaction solution in a centrifuge for centrifugal separation to obtain a solid product.
(4) And (3) washing the solid product with deionized water and ethanol for several times in sequence, and drying in an oven at 80 ℃ for 24h to obtain a precursor for later use.
(5) Placing the precursor in a tubular furnace, calcining the precursor in a nitrogen atmosphere at 500 ℃ for 5 hours at a heating rate of 3 ℃/min, and naturally cooling to room temperature after the calcination is finished to obtain the bimetal niobium oxide composite carbon material: MnNb2O6@C。
And (3) performance testing:
1. XRD tests were performed on the final products prepared in each example and comparative example, and observation was performed under a scanning electron microscope, with the following results:
FIG. 1 shows a multilayer Nb-based MXene (Nb) prepared in accordance with the first example2CTx) XRD pattern (a) and SEM image (b), from which it can be seen that: the multilayer niobium-based MXene is successfully prepared and has an accordion structure unique to MXene.
FIG. 2 shows MnNb prepared in a second embodiment2O6The XRD pattern (a) and SEM image (b) of @ C, from which it can be seen that: MnNb can be demonstrated in comparison with standard pdf cards2O6The @ C preparation was successful and the two-dimensional accordion-like structure of MXene was retained.
FIG. 3 shows SnNb prepared in the third embodiment2O6The XRD pattern (a) and SEM image (b) of @ C, from which it can be seen that: comparison with a standard pdf card can prove SnNb2O6The @ C preparation was successful and the two-dimensional accordion-like structure of MXene was retained.
FIG. 4 is a MgNb prepared in a fourth example2O6The XRD pattern (a) and SEM image (b) of @ C, from which it can be seen that: MgNb can be demonstrated in comparison with standard pdf cards2O6The @ C preparation was successful and the two-dimensional accordion-like structure of MXene was retained.
FIG. 5 shows CoNb prepared in the fifth example2O6The XRD pattern (a) and SEM image (b) of @ C, from which it can be seen that: CoNb can be demonstrated in comparison with standard pdf cards2O6The @ C preparation was successful and the two-dimensional accordion-like structure of MXene was retained. .
Fig. 6 is an XRD pattern (a) and SEM image (b) of the niobium-oxygen mixture prepared in the first comparative example, from which it can be seen that: the samples were not pure phase, mainly Nb2O5There are some other niobia impurities, but the MXene accordion-like structure is retained.
FIG. 7 is an XRD pattern (a) and SEM image (b) of a second comparative manganese niobium oxygen mixture, from which it can be seen that: the samples were not pure phase, mainly Nb2O5And MnO2And other niobia and manganeoxide impurities. But the MXene accordion-like structure is preserved. It can also be shown that outside the range of calcination temperatures claimed in this patent, for example at low temperatures, pure-phase bimetallic niobium oxides cannot be obtained.
2. Assembling and testing the lithium ion battery: electrochemical testing was performed using half-cell button cells. To prepare the working electrode, an active material, acetylene black, and sodium carboxymethylcellulose (CMC) in a mass ratio of 7:2:1 were mixed in deionized water to prepare a uniform slurry. The resulting slurry was then coated onto a copper foil and vacuum dried at 110 ℃ for 11 hours. The half cell was assembled using lithium metal as a counter electrode and then in an argon atmosphere glove box.
MgNb prepared in the fourth example is used in the present invention2O6@ C, accordion-like CoNb prepared in the fifth example2O6@ C, taking the niobium-oxygen mixture prepared in the first comparative proportion and the manganese-niobium-oxygen mixture prepared in the second comparative proportion as active materials respectively to carry out lithium ion battery negative electrode electrochemical performance test.
The final products prepared in the fourth example, the fifth example, the first comparative example, and the second comparative example (5) were used as active materials, and performance tests were performed (see fig. 8 and 9). Wherein:
the current density used for the test of FIG. 8 was 1A g-1It can be seen that: under high current, MgNb prepared in the fourth example2O6When @ C is used as the negative electrode material, 130 mAh g can be maintained after 500 cycles-1High capacity, high current cycle performance ofIs excellent.
The current density used for the test of FIG. 9 was 100mA g-1It can be clearly seen that: the bimetallic niobium oxide composite carbon material prepared in the fourth embodiment and the fifth embodiment has higher specific capacity and more stable cycle performance than the niobium-oxygen mixture and the manganese-niobium-oxygen mixture (mixture of manganese oxide and niobium oxide) prepared in the first comparative example and the second comparative example as the negative electrode material of the lithium ion battery, which shows the stable structure and excellent electrochemical performance of the bimetallic niobium oxide composite carbon material.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The bimetallic niobium oxide has an accordion-shaped lamellar structure of MXene material, and the lamellar component of the structure is bimetallic oxide MNb with a niobite structure2O6Wherein: the MNb2O6M in (3) is selected from any one of Mn, Co, Mg and Sn elements.
2. The bimetallic niobium oxide composite carbon material has an accordion-shaped lamellar structure of MXene material, and the lamellar structure comprises bimetallic oxide MNb2O6And amorphous carbon; wherein: the MNb2O6M in (1) is selected from any one of Mn, Co, Mg and Sn, and the MNb2O6Is of a niobite structure.
3. A method for preparing a bimetallic niobium oxide or a composite carbon material thereof is characterized by comprising the following steps:
(1) adding niobium-based MXene material serving as a niobium source and another alcohol solution containing a metal source into an alcohol solution of urea to obtain a precursor solution for later use; the metal source is selected from any one of Co, Mn, Mg and Sn;
(2) carrying out solvothermal reaction on the precursor solution, separating a solid product in a reaction solution, washing and drying to obtain a precursor for later use;
(3) calcining the precursor in air to obtain a bimetal niobium oxide; or calcining the precursor under the oxygen-isolating condition to obtain the bimetal niobium oxide composite carbon material.
4. The method for preparing a bi-metallic niobium oxide or composite carbon material thereof according to claim 3, wherein in the step (1), the molecular formula of the niobium source is Nb2CTxPreferably, wherein T is a surface group comprising at least one of-OH, -O, -F, -Cl.
5. The method for producing a bimetal niobium oxide or a composite carbon material thereof according to claim 3, wherein in the step (1), the metal source is selected from water-soluble salts of Co, Mn, Mg or Sn elements; preferably at least one of hydrochloride, sulfate, nitrate and acetate.
6. The method for preparing a bi-metallic niobium oxide or a composite carbon material thereof according to claim 3, wherein in the step (1), the alcohol solution of urea is a mixture of urea and ethanol in an amount of 1 to 2 g: mixed solution formed by 40 mL;
or, in the step (1), the molar ratio of niobium element and metal element provided by the niobium source and the metal source in the precursor solution is 2: 1;
preferably, the total concentration of the niobium source and the metal source in the precursor solution is 0.02-0.06 mol/L.
7. The method for preparing a bi-metallic niobium oxide or a composite carbon material thereof according to claim 3, wherein in the step (2), the temperature of the solvothermal reaction is 150 to 180 ℃, and the reaction time is 12 to 18 hours.
8. The method for preparing the bi-metal niobium oxide or the composite carbon material thereof according to claim 3, wherein in the step (2), the solid product in the reaction solution is separated by filtration or centrifugation, and then the mixture is sequentially washed with ethanol and deionized water and dried at 50-80 ℃ for 10-24 hours to obtain the precursor.
9. The method for preparing a bi-metallic niobium oxide or a composite carbon material thereof according to claim 3, wherein in the step (3), the calcination temperature is 700 to 900 ℃, and the calcination time is 4 to 6 hours;
preferably, in the step (3), the oxygen-isolating condition provides an oxygen-isolating reaction environment by using inert gas or nitrogen as a protective gas.
10. Use of the bi-metallic niobium oxide of claim 1 or the bi-metallic niobium oxide composite carbon material of claim 2 or the bi-metallic niobium oxide prepared by the method of any one of claims 3 to 9 or the composite carbon material thereof in energy storage components, preferably as negative electrode material for lithium batteries.
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