CN114203983B - Preparation method of porous zinc molybdate/zinc oxide/graphene composite material and application of porous zinc molybdate/zinc oxide/graphene composite material to negative electrode of lithium ion battery - Google Patents
Preparation method of porous zinc molybdate/zinc oxide/graphene composite material and application of porous zinc molybdate/zinc oxide/graphene composite material to negative electrode of lithium ion battery Download PDFInfo
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Abstract
The invention belongs to the technical field of nano composite material preparation, and relates to a preparation method of a porous zinc molybdate/zinc oxide/graphene composite material, which comprises the following steps: respectively dissolving tris (hydroxymethyl) aminomethane hydrochloride and cationic polyelectrolyte in a sodium chloride solution, adding a graphene oxide dispersion solution, stirring, centrifugally separating, washing, and ultrasonically dispersing a precipitate in deionized water to obtain a cationic polyelectrolyte-modified graphene oxide dispersion solution with the concentration of 1-3 mg/mL; adding a zinc salt solution and a potassium octacyano molybdate solution in sequence, stirring, centrifugally separating, washing and freeze-drying; calcining in inert gas to obtain the final product. The porous zinc molybdate/zinc oxide/graphene composite material is prepared by using an ion exchange-thermal reduction two-step method, the operation process is simple and easy to implement, the reaction time is short, the environment is protected, and the porous zinc molybdate/zinc oxide/graphene composite material is safe to use as a lithium ion battery cathode material and shows excellent electrochemical lithium storage performance by adjusting the factors such as the using amount of graphene oxide, the calcination temperature and the like.
Description
Technical Field
The invention belongs to the technical field of nano composite material preparation, relates to a composite electrode material, and particularly relates to porous zinc molybdate/zinc oxide/graphene (Zn) 2 Mo 3 O 8 Preparation method of/ZnO/graphene) composite material and application of the composite material to lithium ion battery negative electrodes.
Background
With the increasing energy crisis and environmental issues, efficient use of renewable energy sources is critical to sustainable development. Development of low-cost, advanced large-scale energy storage and conversion equipment is particularly urgent. Lithium Ion Batteries (LIBs) are a very wide battery technology currently studied, have the advantages of high energy density, good safety, no memory effect, long cycle life and the like, and are widely applied to the field of portable electronic products. In recent years, the new energy automobile market has become a main power for the rapid development of the global lithium battery industry. However, commercial lithium ion batteries employing intercalated positive and graphite negative electrodes are approaching their fundamental limits, primarily in terms of specific capacity. Therefore, the construction of next-generation lithium ion batteries with higher energy density, higher safety, lower cost, and longer cycle life is attracting great attention from countries around the world.
Currently, commercial graphite anodes offer a relatively low weight/volume capacity (372 mA h g) -1 And 735mA h cm -3 ) Also, the energy density (Wh kg) of commercial lithium ion battery systems is limited -1 And Wh. L -1 ). For this reason, it is necessary to develop advanced anode materials, including various conversion-type and alloy-type high-capacity anode materials, to meet the market demand of rechargeable batteries with improved energy density. High capacity conversion type anode materials, such as transition metal oxides, exhibit higher theoretical capacities than graphite anodes in both weight and volume terms. However, metal oxides have poor conductivity and large volume change in the continuous charging and discharging process, which easily causes the problems of low battery cycle stability, poor rate performance and the like, and greatly limits the practical application of the materials. According to research reports, the lithium storage performance of the metal oxide can be comprehensively improved from two aspects of micro-nano structure design and component regulation: relieving the volume expansion of the electrode material in the lithium intercalation/lithium deintercalation process by utilizing the hollow/porous nano structure; compounding with carbon material with good conductivity (such as carbon nanotube and graphene) to improve conductivity of oxide electrodeStructural stability, and the electrochemical performance of the material is improved by utilizing the synergy of bimetal. Thus, it is expected that the cycle and rate performance of the metal oxide negative electrode can be improved by the combination of the mixed metal oxide with graphene.
Disclosure of Invention
In view of the above-mentioned shortcomings in the prior art, the present invention aims to provide a porous zinc molybdate/zinc oxide/graphene (Zn) 2 Mo 3 O 8 Preparation method of/ZnO/graphene) composite material.
Technical scheme
A preparation method of a porous zinc molybdate/zinc oxide/graphene composite material comprises the following steps:
(1) Ultrasonically dispersing graphite oxide in deionized water to obtain 1-3 mg/mL graphene oxide dispersion liquid;
(2) Respectively dissolving tris (hydroxymethyl) aminomethane hydrochloride and a cationic polyelectrolyte in a sodium chloride solution, adding a graphene oxide dispersion solution, stirring for 10-14 h, preferably 12h, performing centrifugal separation and deionized water washing, and ultrasonically dispersing the precipitate in deionized water to obtain a cationic polyelectrolyte-modified graphene oxide dispersion solution with a concentration of 1-3 mg/mL, wherein the mass ratio of the cationic polyelectrolyte to tris (hydroxymethyl) aminomethane hydrochloride to sodium chloride is 25;
(3) Preparing a porous zinc molybdate/graphene composite negative electrode material;
(3-1) adding zinc salt into deionized water, stirring and dissolving to obtain 0.01-0.15 mol/L solution a, preferably 0.1mol/L;
(3-2) reacting potassium octacyanomolybdate (K) 4 [Mo(CN) 8 ]·2H 2 O) is added into deionized water, stirred and dissolved to obtain 0.01 to 0.03mol/L solution b, preferably 0.025mol/L solution b;
(3-3) adding the solution a into the cationic polyelectrolyte modified graphene oxide dispersion liquid, and stirring for 10-14 h, preferably 12h; adding the solution b, stirring for 1-6 h, preferably 4h, performing centrifugal separation, washing precipitates with deionized water, and freeze-drying; wherein the volume ratio of the solution a to the solution b to the cationic polyelectrolyte-modified graphene oxide dispersion liquid is 2:1-4:7, preferably 2;
and (3-2) heating the product in an inert gas at 600-800 ℃ for 2-6 h, preferably at 700 ℃ for 2h to obtain the porous zinc molybdate/zinc oxide/graphene composite material.
In a preferred embodiment of the present invention, the cationic polyelectrolyte in step (2) is one of polydiallyldimethylammonium chloride (PDDA), cationic Polyacrylamide (CPAM) or polyacrylamide hydrochloride (PAH), preferably polydiallyldimethylammonium chloride (PDDA), wherein the molecular weight of PDDA is less than 100000.
In the preferred embodiment of the invention, the concentration of the sodium chloride solution in the step (2) is 0.03-0.06 mol/L, preferably 0.05mol/L, and the freeze-drying temperature is-40 to-60 ℃, preferably-50 ℃.
In a preferred embodiment of the present invention, the zinc salt in step (3-1) is zinc acetate ((CH) 3 COO) 2 Zn·2H 2 O), zinc chloride (ZnCl) 2 ) Or zinc nitrate (Zn (NO) 3 ) 2 ·6H 2 O), preferably zinc acetate ((CH) 3 COO) 2 Zn·2H 2 O)。
In the preferred embodiment of the invention, the molar ratio of the potassium octacyano molybdate to the zinc acetate in the step (3-2) is 1:2-1:6, preferably 1:4.
In the preferred embodiment of the invention, the inert gas in the step (3-3) is argon, and the heating rate is 2-5 ℃/min, preferably 2 ℃/min.
The graphite oxide takes natural crystalline flake graphite as a raw material, and is oxidized by a Hummers method: placing a dry three-neck flask (500 mL) in an HJ-3 constant-temperature magnetic stirrer, adding 80mL 98% concentrated sulfuric acid, cooling to 0 ℃ in an ice bath, adding 2g of natural crystalline flake graphite while stirring, stirring uniformly, and slowly adding 4g of NaNO 3 And 10g KMnO 4 The reaction mixture was stirred for 4 hours while the temperature of the reaction mixture was controlled to 10 ℃ or lower. Adjusting the temperature of the HJ-3 constant-temperature magnetic stirrer, raising the temperature of the reaction solution to about 35 ℃, and reacting for 1 hour at the temperature. Finally, 160mL of deionized water was added to the reaction mixture, and the temperature of the reaction mixture was controlled at 100 ℃ toStirring for 30min. 10mL of 30% H was slowly added 2 O 2 Cooling, removing incompletely oxidized black granules, centrifuging with 5% HCl, dissolving the product in deionized water, and dialyzing until the solution is free of Cl - Freeze-drying at-50 ℃.
Potassium octacyanomolybdate (K) according to the invention 4 [Mo(CN) 8 ]·2H 2 O), the preparation method comprises the following steps: to a 250mL round bottom flask, 36g (0.15 mol) of Na was added in order 2 MoO 4 ·2H 2 O,175g KCN(2.7mol)，18g(0.33mol) KBH 4 And 300mL of distilled water, and dissolved with stirring. After 1 hour of reaction, 140mL of concentrated acetic acid was added to the above solution with stirring, the color of the solution changed from colorless to green and finally to yellow, and then the solution was heated in a water bath for 20 minutes. The solution was cooled to room temperature and 500mL ethanol was added to allow formation of K 4 [Mo(CN) 8 ]·2H 2 And (4) rapidly settling the O, wherein the product is slightly green, and continuously purifying. Dissolving the product in 30mL distilled water, adding active carbon, boiling for 10 min, filtering, adding 200mL ethanol to the filtrate to allow the product to settle quickly, and obtaining bright yellow crystal product K 4 [Mo(CN) 8 ]·2H 2 O。
According to the porous zinc molybdate/zinc oxide/graphene composite material prepared by the method, a porous micron sheet consisting of zinc molybdate/zinc oxide nano particles is tightly attached to a reduced graphene oxide skeleton, and the particle size of the nano particles is 30-60 nm.
The invention also aims to apply the prepared porous zinc molybdate/zinc oxide/graphene composite material to a lithium ion battery cathode.
Advantageous effects
According to the invention, by utilizing an ion exchange-thermal reduction two-step method, factors such as the dosage of graphene oxide, the calcination temperature and the like are adjusted to prepare the porous zinc molybdate/zinc oxide/graphene composite negative electrode material, and the composite material shows excellent electrochemical lithium storage performance as a lithium ion battery negative electrode material. The method has the advantages of simple and easy operation process, short reaction time, environmental protection, safety, low cost and easy industrial implementation. The material has excellent lithium storage performance and is expected to be used as a negative electrode material of a lithium ion battery.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the porous zinc molybdate/zinc oxide/graphene composite nanomaterial prepared in example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the porous zinc molybdate/zinc oxide/graphene composite nanomaterial prepared in example 1.
FIG. 3 is a Transmission Electron Microscope (TEM) photograph of the porous zinc molybdate/zinc oxide/graphene composite nanomaterial prepared in example 1.
FIG. 4 shows that the porous zinc molybdate/zinc oxide/graphene composite nanomaterial prepared in example 1 is used as a negative electrode material of a lithium ion battery at a current density of 0.2 A.g -1 Cycle performance graph below.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
A preparation method of a porous zinc molybdate/zinc oxide/graphene composite material comprises the following steps:
A. ultrasonically dispersing 70mg of graphite oxide in 35ml of deionized water, and ultrasonically treating for 2 hours to obtain a graphene oxide dispersion liquid;
B. preparing 0.05mol/L sodium chloride solution (containing 0.1g of sodium chloride and 50ml of deionized water), respectively dissolving 1.25g of polydiallyldimethylammonium chloride (PDDA) and 0.2g of tris (hydroxymethyl) aminomethane hydrochloride in the sodium chloride solution, adding the graphene oxide dispersion liquid, stirring for 12h, performing centrifugal separation, washing for 5 times with deionized water, ultrasonically dispersing the precipitate in 35ml of deionized water, and stirring for 1h to obtain a PDDA modified graphene oxide dispersion liquid;
C. dissolving 0.13g of potassium octacyanomolybdate into 10ml of solution, adding the solution into the PDDA modified graphene oxide dispersion solution, stirring the mixture for reaction for 12 hours, then adding a zinc acetate solution (containing 0.22g of zinc acetate and 10ml of deionized water), stirring for 4 hours, then carrying out centrifugal separation, washing the product with deionized water, and carrying out freeze drying at (-50 ℃) to obtain a brown yellow precursor product;
D. and placing the brown yellow precursor product into a porcelain boat, and calcining at 700 ℃ in a tube furnace filled with argon at the heating rate of 2 ℃/min for 2h to obtain the final product, namely the porous zinc molybdate/zinc oxide/graphene composite nano material.
Fig. 1 is an XRD chart of the prepared product, and the positions of characteristic peaks of the product are respectively consistent with those of hexagonal phase zinc molybdate and hexagonal phase zinc oxide standard cards, which indicates that the porous zinc molybdate/zinc oxide/graphene composite nanomaterial is successfully prepared.
Fig. 2 is an SEM image of the prepared product, and it can be observed that zinc molybdate/zinc oxide micro-platelets having rough surfaces are dispersed on the reduced graphene oxide sheets.
Fig. 3 is a TEM image of the prepared product, and it can be seen that the porous zinc molybdate/zinc oxide nanosheets are composed of a plurality of nanoparticles having abundant pores between the particles and closely adhered to the surface of the reduced graphene oxide, wherein the nanoparticles have a particle size of 30 to 60nm.
FIG. 4 is a cycle performance diagram of the prepared porous zinc molybdate/zinc oxide/graphene composite nanomaterial as a lithium ion battery negative electrode material, and shows that the synthesized material has high specific capacity and cycle performance, and the current density is 0.2 A.g -1 After 100 cycles, the capacity reaches 960mA h.g -1 。
Example 2
A preparation method of a porous zinc molybdate/zinc oxide/graphene composite material comprises the following steps:
A. ultrasonically dispersing 60mg of graphite oxide in 30ml of deionized water, and ultrasonically treating for 2 hours to obtain a graphene oxide dispersion liquid;
B. preparing 0.05mol/L sodium chloride solution (containing 0.1g of sodium chloride and 50ml of deionized water), respectively dissolving 1.25g of polydiallyldimethylammonium chloride (PDDA) and 0.2g of tris (hydroxymethyl) aminomethane hydrochloride in the sodium chloride solution, adding the graphene oxide dispersion liquid, stirring for 12h, performing centrifugal separation, washing for 5 times with deionized water, ultrasonically dispersing the precipitate in 30ml of deionized water, and stirring for 1h to obtain a PDDA modified graphene oxide dispersion liquid;
C. dissolving 0.13g of potassium octacyanomolybdate into 10ml of solution, adding the solution into the PDDA modified graphene oxide dispersion solution, stirring the mixture for reaction for 12 hours, then adding a zinc acetate solution (containing 0.22g of zinc acetate and 10ml of deionized water), stirring for 4 hours, then carrying out centrifugal separation, washing the product with deionized water, and carrying out freeze drying at (-50 ℃) to obtain a brown yellow precursor product;
D. and placing the brown yellow precursor product into a porcelain boat, and calcining at 700 ℃ in a tubular furnace filled with argon at the heating rate of 2 ℃/min for 2h to obtain the final product, namely the porous zinc molybdate/zinc oxide/graphene composite nano material.
The prepared porous zinc molybdate/zinc oxide/graphene composite nano material is used as a lithium ion battery cathode material, and the current density is 0.2 A.g -1 At the time of 100 cycles, the capacity is as high as 1000mA h.g -1 。
Example 3
A preparation method of a porous zinc molybdate/zinc oxide/graphene composite material comprises the following steps:
A. ultrasonically dispersing 90mg of graphite oxide in 45ml of deionized water, and ultrasonically treating for 2 hours to obtain a graphene oxide dispersion liquid;
B. preparing 0.05mol/L sodium chloride solution (containing 0.1g of sodium chloride and 50ml of deionized water), respectively dissolving 1.25g of polydiallyldimethylammonium chloride (PDDA) and 0.2g of tris (hydroxymethyl) aminomethane hydrochloride in the sodium chloride solution, adding the graphene oxide dispersion liquid, stirring for 12 hours, carrying out centrifugal separation, washing for 5 times with the deionized water, ultrasonically dispersing the precipitate in 45ml of deionized water, and stirring for 1 hour to obtain the PDDA modified graphene oxide dispersion liquid;
C. dissolving 0.13g of potassium octacyanomolybdate into 10ml of solution, adding the solution into the PDDA modified graphene oxide dispersion solution, stirring the mixture for reaction for 12 hours, then adding a zinc acetate solution (containing 0.22g of zinc acetate and 10ml of deionized water), stirring for 4 hours, then carrying out centrifugal separation, washing the product with deionized water, and carrying out freeze drying at (-50 ℃) to obtain a brown yellow precursor product;
D. and placing the brown yellow precursor product into a porcelain boat, and calcining at 700 ℃ in a tubular furnace filled with argon at the heating rate of 2 ℃/min for 2h to obtain the final product, namely the porous zinc molybdate/zinc oxide/graphene composite nano material.
The prepared porous zinc molybdate/zinc oxide/graphene composite nano material is used as a lithium ion battery cathode material, and the current density is 0.2 A.g -1 After 100 cycles, the capacity is as high as 800mA h.g -1 。
Example 4
A preparation method of a porous zinc molybdate/zinc oxide/graphene composite material comprises the following steps:
A. ultrasonically dispersing 70mg of graphite oxide in 35ml of deionized water, and ultrasonically treating for 2 hours to obtain a graphene oxide dispersion liquid;
B. preparing 0.05mol/L sodium chloride solution (containing 0.1g of sodium chloride and 50ml of deionized water), respectively dissolving 1.25g of polydiallyldimethylammonium chloride (PDDA) and 0.2g of tris (hydroxymethyl) aminomethane hydrochloride in the sodium chloride solution, adding the graphene oxide dispersion liquid, stirring for 12h, performing centrifugal separation, washing for 5 times with deionized water, ultrasonically dispersing the precipitate in 35ml of deionized water, and stirring for 1h to obtain a PDDA modified graphene oxide dispersion liquid;
C. dissolving 0.13g of potassium octacyanomolybdate into 10ml of solution, adding the solution into the PDDA modified graphene oxide dispersion solution, stirring the mixture for reaction for 12 hours, then adding a zinc acetate solution (containing 0.22g of zinc acetate and 10ml of deionized water), stirring for 4 hours, then carrying out centrifugal separation, washing the product with deionized water, and carrying out freeze drying at (-50 ℃) to obtain a brown yellow precursor product;
D. and placing the brown yellow precursor product into a porcelain boat, and calcining at 600 ℃ in a tubular furnace filled with argon at the heating rate of 2 ℃/min for 2h to obtain the final product, namely the porous zinc molybdate/zinc oxide/graphene composite nano material.
The prepared porous zinc molybdate/zinc oxide/graphene composite nano material is used as a lithium ion battery cathode material, and the current density is 0.2 A.g -1 After 100 cycles, the capacity reaches 920mA h.g -1 。
Example 5
A preparation method of a porous zinc molybdate/zinc oxide/graphene composite material comprises the following steps:
A. ultrasonically dispersing 70mg of graphite oxide in 35ml of deionized water, and ultrasonically treating for 2 hours to obtain a graphene oxide dispersion liquid;
B. preparing 0.05mol/L sodium chloride solution (containing 0.1g of sodium chloride and 50ml of deionized water), respectively dissolving 1.25g of poly (diallyldimethyl) ammonium chloride (PDDA) and 0.2g of tris (hydroxymethyl) aminomethane hydrochloride in the sodium chloride solution, adding the graphene oxide dispersion liquid, stirring for 12 hours, carrying out centrifugal separation, washing for 5 times by using the deionized water, ultrasonically dispersing the precipitate in 35ml of deionized water, and stirring for 1 hour to obtain a PDDA modified graphene oxide dispersion liquid;
C. dissolving 0.13g of potassium octacyanomolybdate into 10ml of solution, adding the solution into the PDDA modified graphene oxide dispersion solution, stirring the mixture for reaction for 12 hours, then adding a zinc acetate solution (containing 0.22g of zinc acetate and 10ml of deionized water), stirring for 4 hours, then carrying out centrifugal separation, washing the product with deionized water, and carrying out freeze drying at (-50 ℃) to obtain a brown yellow precursor product;
D. and placing the brown yellow precursor product into a porcelain boat, and calcining at 800 ℃ in a tube furnace filled with argon at the heating rate of 2 ℃/min for 2h to obtain the final product, namely the porous zinc molybdate/zinc oxide/graphene composite nano material.
The prepared three-dimensional porous germanium/graphene composite nano material is used as a lithium ion battery cathode material, and the current density is 0.2A. G -1 After 100 cycles, the capacity reaches 975mA h g -1 。
Example 6
A preparation method of a porous zinc molybdate/zinc oxide/graphene composite material comprises the following steps:
A. ultrasonically dispersing 70mg of graphite oxide in 35ml of deionized water, and ultrasonically treating for 2 hours to obtain a graphene oxide dispersion liquid;
B. preparing 0.05mol/L sodium chloride solution (containing 0.1g of sodium chloride and 50ml of deionized water), respectively dissolving 1.25g of polydiallyldimethylammonium chloride (PDDA) and 0.2g of tris (hydroxymethyl) aminomethane hydrochloride in the sodium chloride solution, adding the graphene oxide dispersion liquid, stirring for 12h, performing centrifugal separation, washing for 5 times with deionized water, ultrasonically dispersing the precipitate in 35ml of deionized water, and stirring for 1h to obtain a PDDA modified graphene oxide dispersion liquid;
C. dissolving 0.13g of potassium octacyanomolybdate into 10ml of solution, adding the solution into the PDDA modified graphene oxide dispersion solution, stirring the mixture for reaction for 12 hours, then adding a zinc acetate solution (containing 0.22g of zinc acetate and 10ml of deionized water), stirring for 4 hours, then carrying out centrifugal separation, washing the product with deionized water, and carrying out freeze drying at (-50 ℃) to obtain a brown yellow precursor product;
D. and placing the brown yellow precursor product into a porcelain boat, and calcining at 700 ℃ in a tube furnace filled with argon at the heating rate of 2 ℃/min for 4h to obtain the final product, namely the porous zinc molybdate/zinc oxide/graphene composite nano material.
The prepared three-dimensional porous germanium/graphene composite nano material is used as a lithium ion battery cathode material, and the current density is 0.2A. G -1 After 100 cycles, the capacity is up to 940mA h.g -1 。
Example 7
A preparation method of a porous zinc molybdate/zinc oxide/graphene composite material comprises the following steps:
A. ultrasonically dispersing 70mg of graphite oxide in 35ml of deionized water, and ultrasonically dispersing for 2 hours to obtain graphene oxide dispersion;
B. preparing 0.05mol/L sodium chloride solution (containing 0.1g of sodium chloride and 50ml of deionized water), respectively dissolving 1.25g of polydiallyldimethylammonium chloride (PDDA) and 0.2g of tris (hydroxymethyl) aminomethane hydrochloride in the sodium chloride solution, adding the graphene oxide dispersion liquid, stirring for 12h, performing centrifugal separation, washing for 5 times with deionized water, ultrasonically dispersing the precipitate in 35ml of deionized water, and stirring for 1h to obtain a PDDA modified graphene oxide dispersion liquid;
C. dissolving 0.13g of potassium octacyanomolybdate into 10ml of solution, adding the solution into the PDDA modified graphene oxide dispersion solution, stirring the mixture for reaction for 12 hours, then adding a zinc acetate solution (containing 0.22g of zinc acetate and 10ml of deionized water), stirring for 4 hours, then carrying out centrifugal separation, washing the product with deionized water, and carrying out freeze drying at (-50 ℃) to obtain a brown yellow precursor product;
D. and placing the brown yellow precursor product into a porcelain boat, and calcining at 700 ℃ in a tubular furnace filled with argon at the heating rate of 2 ℃/min for 6h to obtain the final product, namely the porous zinc molybdate/zinc oxide/graphene composite nano material.
The prepared three-dimensional porous germanium/graphene composite nano material is used as a lithium ion battery cathode material, and the current density is 0.2A g -1 The capacity is up to 970mA h g after 100 cycles -1 。
Example 8
A preparation method of a porous zinc molybdate/zinc oxide/graphene composite material comprises the following steps:
A. ultrasonically dispersing 70mg of graphite oxide in 35ml of deionized water, and ultrasonically treating for 2 hours to obtain a graphene oxide dispersion liquid;
B. preparing 0.05mol/L sodium chloride solution (containing 0.1g of sodium chloride and 50ml of deionized water), respectively dissolving 1.25g of polydiallyldimethylammonium chloride (PDDA) and 0.2g of tris (hydroxymethyl) aminomethane hydrochloride in the sodium chloride solution, adding the graphene oxide dispersion liquid, stirring for 12h, performing centrifugal separation, washing for 5 times with deionized water, ultrasonically dispersing the precipitate in 35ml of deionized water, and stirring for 1h to obtain a PDDA modified graphene oxide dispersion liquid;
C. dissolving 0.13g of potassium octacyanomolybdate into 10ml of solution, adding the solution into the PDDA modified graphene oxide dispersion solution, stirring the mixture for reaction for 12 hours, then adding a zinc acetate solution (containing 0.22g of zinc acetate and 10ml of deionized water), stirring for 4 hours, then carrying out centrifugal separation, washing the product with deionized water, and carrying out freeze drying at (-50 ℃) to obtain a brown yellow precursor product;
D. and placing the brown yellow precursor product into a porcelain boat, and calcining at 700 ℃ in a tube furnace filled with argon at the heating rate of 5 ℃/min for 2h to obtain the final product, namely the porous zinc molybdate/zinc oxide/graphene composite nano material.
The prepared three-dimensional porous germanium/graphene composite nano material is used as a lithium ion battery cathode material, and the current density is 0.2A g -1 After 100 cycles, the capacity is up to 950mA h.g -1 。
Example 9
A preparation method of a porous zinc molybdate/zinc oxide/graphene composite material comprises the following steps:
A. ultrasonically dispersing 70mg of graphite oxide in 35ml of deionized water, and ultrasonically treating for 2 hours to obtain a graphene oxide dispersion liquid;
B. preparing 0.05mol/L sodium chloride solution (containing 0.1g of sodium chloride and 50ml of deionized water), respectively dissolving 1.25g of polydiallyldimethylammonium chloride (PDDA) and 0.2g of tris (hydroxymethyl) aminomethane hydrochloride in the sodium chloride solution, adding the graphene oxide dispersion liquid, stirring for 12h, performing centrifugal separation, washing for 5 times with deionized water, ultrasonically dispersing the precipitate in 35ml of deionized water, and stirring for 1h to obtain a PDDA modified graphene oxide dispersion liquid;
C. dissolving 0.13g of potassium octacyano molybdate into 10ml of solution, adding the solution into the PDDA modified graphene oxide dispersion solution, stirring the mixture to react for 12 hours, then adding a zinc acetate solution (containing 0.22g of zinc acetate and 10ml of deionized water), stirring for 4 hours, then carrying out centrifugal separation, washing the product with the deionized water, and carrying out freeze drying (-50 ℃) to obtain a brown-yellow precursor product;
D. and placing the brown yellow precursor product into a porcelain boat, and calcining at 700 ℃ in a tubular furnace filled with argon, wherein the heating rate is 3 ℃/min, and the calcining time is 2h, so as to obtain the final product, namely the porous zinc molybdate/zinc oxide/graphene composite nano material.
The prepared three-dimensional porous germanium/graphene composite nano material is used as a lithium ion battery cathode material, and the current density is 0.2A g -1 After 100 cycles, the capacity reaches 945mA h g -1 。
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (20)
1. A preparation method of a porous zinc molybdate/zinc oxide/graphene composite material is characterized by comprising the following steps:
(1) Ultrasonically dispersing graphite oxide in deionized water to obtain 1-3 mg/mL graphene oxide dispersion liquid;
(2) Respectively dissolving tris (hydroxymethyl) aminomethane hydrochloride and a cationic polyelectrolyte in a sodium chloride solution, adding a graphene oxide dispersion solution, stirring for 10-14 h, performing centrifugal separation and deionized water washing, and ultrasonically dispersing the precipitate in deionized water to obtain a cationic polyelectrolyte modified graphene oxide dispersion solution with the concentration of 1-3 mg/mL, wherein the mass ratio of the cationic polyelectrolyte to the tris (hydroxymethyl) aminomethane hydrochloride to the sodium chloride is 25-5:2, and the volume ratio of the sodium chloride solution to the graphene oxide dispersion solution is 12;
(3) Preparing a porous zinc molybdate/zinc oxide/graphene composite material:
(3-1) adding zinc acetate (CH) 3 COO) 2 Zn·2H 2 Adding O into deionized water, stirring and dissolving to obtain 0.1-0.15 mol/L solution a;
(3-2) reacting potassium octacyanomolybdate K 4 [Mo(CN) 8 ]·2H 2 Adding O into deionized water, stirring and dissolving to obtain 0.01-0.03 mol/L solution b;
(3-3) adding the solution a into the cationic polyelectrolyte modified graphene oxide dispersion liquid, and stirring for 10-14 h; adding the solution b, stirring for 1-6 h, performing centrifugal separation, washing precipitates with deionized water, and freeze-drying; the volume ratio of the solution a to the solution b to the cationic polyelectrolyte modified graphene oxide dispersion liquid is 2:1-4:7; the molar ratio of the potassium octacyano molybdate to the zinc acetate is 1:2-1:6;
(3-4) heating the product in an inert gas at 600-800 ℃ for 2-6 h to obtain the porous zinc molybdate/zinc oxide/graphene composite material, wherein the porous zinc molybdate/zinc oxide/graphene composite material is Zn 2 Mo 3 O 8 The porous microchip consisting of zinc molybdate/zinc oxide nanoparticles is tightly attached to a reduced graphene oxide skeleton, and the particle size of the nanoparticles is 30-60 nm.
2. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 1, wherein the method comprises the following steps: and (2) respectively dissolving the tris (hydroxymethyl) aminomethane hydrochloride and the cationic polyelectrolyte in a sodium chloride solution, adding the graphene oxide dispersion liquid, and stirring for 12 hours.
3. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 1, wherein the method comprises the following steps: the mass ratio of the cationic polyelectrolyte, the tris (hydroxymethyl) aminomethane hydrochloride and the sodium chloride in the step (2) is 25.
4. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 1, wherein the method comprises the following steps: the cationic polyelectrolyte in the step (2) is one of poly (diallyldimethylammonium chloride) (PDDA), cationic Polyacrylamide (CPAM) or polyacrylamide hydrochloride (PAH).
5. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 4, wherein the method comprises the following steps: the cationic polyelectrolyte in the step (2) is poly diallyl dimethyl ammonium chloride PDDA, and the molecular weight is less than 100000.
6. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 1, wherein the method comprises the following steps: the concentration of the sodium chloride solution in the step (2) is 0.03-0.06 mol/L.
7. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 6, wherein the method comprises the following steps: the concentration of the sodium chloride solution in the step (2) is 0.05 mol/L.
8. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 1, wherein the method comprises the following steps: adding zinc acetate (CH) as described in step (3-1) 3 COO) 2 Zn·2H 2 Adding O into deionized water, stirring and dissolving to obtain 0.1mol/L solution a.
9. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 1, wherein the method comprises the following steps: the potassium octacyanomolybdate K in the step (3-2) 4 [Mo(CN) 8 ]·2H 2 Adding O into deionized water, stirring and dissolving to obtain 0.025mol/L solution b.
10. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 1, wherein the method comprises the following steps: and (4) adding the solution a into the cationic polyelectrolyte modified graphene oxide dispersion liquid, and stirring for 12 hours.
11. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 1, wherein the method comprises the following steps: and (4) adding the solution b into the solution obtained in the step (3-3), and stirring for 4 hours.
12. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 1, wherein the method comprises the following steps: the freeze drying temperature in the step (3-3) is-60 to-40 ℃.
13. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 12, wherein the method comprises the following steps: the freeze-drying temperature in the step (3-3) is-50 ℃.
14. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 1, wherein the method comprises the following steps: and (3) the volume ratio of the solution a to the solution b to the cationic polyelectrolyte-modified graphene oxide dispersion liquid in the step (3-3) is 2.
15. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 1, wherein the method comprises the following steps: the molar ratio of the potassium octacyanomolybdate to the zinc acetate in the step (3-3) is 1:4.
16. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 1, wherein the method comprises the following steps: and (4) heating the product in the step (3-4) in an inert gas at 700 ℃ for 2h.
17. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 1, wherein the method comprises the following steps: and (4) the inert gas in the step (3-4) is argon, and the heating rate is 2-5 ℃/min.
18. The method for preparing the porous zinc molybdate/zinc oxide/graphene composite material according to claim 17, wherein the method comprises the following steps: in the step (3-4), the heating rate is 2 ℃/min.
19. A porous zinc molybdate/zinc oxide/graphene composite material prepared according to the method of any one of claims 1 to 18.
20. Use of the porous zinc molybdate/oxide/graphene composite material according to claim 19, wherein: the method is applied to the negative electrode of the lithium ion battery.
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