CN116960296A - Capacitance-enhanced three-dimensional feather-shaped zinc cobalt oxide lithium battery anode material and preparation method thereof - Google Patents

Capacitance-enhanced three-dimensional feather-shaped zinc cobalt oxide lithium battery anode material and preparation method thereof Download PDF

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CN116960296A
CN116960296A CN202310866873.XA CN202310866873A CN116960296A CN 116960296 A CN116960296 A CN 116960296A CN 202310866873 A CN202310866873 A CN 202310866873A CN 116960296 A CN116960296 A CN 116960296A
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znco
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foam nickel
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郑国旭
黄新哲
袁卓
吴蕊
郑文涛
谢镇鸿
王秋雯
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Harbin University of Science and Technology
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Abstract

The invention relates to a capacitance-enhanced three-dimensional feather-shaped zinc cobalt oxide lithium battery negative electrode material and a preparation method thereof, and relates to the field of lithium batteries, wherein Co sequentially grows on foam nickel through a simple secondary hydrothermal method 3 O 4 Nanorods and ZnCo 2 O 4 The nanowire is obtained, and the special three-dimensional feather-like structure is electrically obtainedCapacity enhanced Co 3 O 4 /ZnCo 2 O 4 The preparation method of the/NF is simple, low in cost, less in time consumption and excellent in electrochemical performance. Capacitance enhanced Co 3 O 4 /ZnCo 2 O 4 The capacity of/NF is larger and the stability is better. The large capacitance characteristic ratio ensures that the quick charge and discharge capacity of the lithium ion battery is better than that of a common lithium ion battery, and the lithium ion battery is a cathode material of a high-performance lithium ion battery which has potential to replace graphite materials.

Description

Capacitance-enhanced three-dimensional feather-shaped zinc cobalt oxide lithium battery anode material and preparation method thereof
Technical Field
The invention belongs to the field of lithium batteries, and particularly relates to a capacitance-enhanced three-dimensional feather-shaped zinc cobalt oxide lithium battery anode material and a preparation method thereof.
Background
Lithium batteries are a type of battery using a nonaqueous electrolyte solution, which uses lithium metal or lithium alloy as a positive/negative electrode material, and can be classified into lithium metal batteries and lithium ion batteries. The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, electrolyte and a diaphragm, wherein the negative electrode material is used for storing and releasing energy, and has a remarkable influence on the performance of the lithium ion battery. The traditional lithium ion battery mostly adopts graphite as a negative electrode material, but the capacity of the graphite is lower, the stability is poor, and the ever-increasing requirement of people on the performance of the lithium ion battery can not be met. The transition metal oxide has higher theoretical capacity and better conductivity due to self alloying/dealloying reaction. Wherein cobalt-based transition metal oxide and zinc-cobalt transition metal oxide have the potential to replace graphite materials, but both of them are not sufficiently stable, and because of Co 3 O 4 And ZnCo 2 O 4 The crystal structure is similar, the theoretical capacity is high, the conductivity is good, and the electrochemical activity is excellent, so that Co is compounded on the foam nickel 3 O 4 And ZnCo 2 O 4 . In addition, the research of the capacitance-enhanced lithium ion battery is less, and the capacitance-enhanced lithium ion battery has the advantages of higher charge and discharge speed, high working efficiency, large energy ratio, long cycle life and greennessEnvironmental protection, the application scene of the capacitance-enhanced lithium battery has a certain gap, so the capacitance-enhanced Co is designed 3 O 4 /ZnCo 2 O 4 the/NF is necessary as a negative electrode material of a lithium ion battery.
Disclosure of Invention
The invention aims to solve the defects of the existing lithium ion battery cathode material and manufacture a novel lithium ion battery cathode material with a three-dimensional feather structure, wherein the three-dimensional feather structure is composed of one-dimensional nanorods and nanowires, the synergistic effect of two different materials provides excellent stability and capacity, the tight interweaving of the two materials accelerates the transportation efficiency of lithium ions, the capacitance characteristic occupation ratio of the materials is greatly improved, and the electrochemical performance of the materials is further improved.
The invention relates to a capacitance-enhanced three-dimensional feather-shaped zinc cobalt oxide lithium battery anode material, which is prepared from Co 3 O 4 And ZnCo 2 O 4 Is prepared by the method;
the lithium battery anode material is of a three-dimensional feather-like structure, and the specific surface area is 63-66 m 2 ·g -1 The porosity is 30% -40%.
Further, the three-dimensional feather-like structure is Co 3 O 4 /ZnCo 2 O 4 the/NF is composed of one-dimensional Co 3 O 4 Nanorods and one-dimensional ZnCo 2 O 4 The nanowire is formed by combining.
Further, the one-dimensional Co 3 O 4 The nanorods consist of an arrangement of nanocrystalline grains with an average diameter of 28-32nm, co 3 O 4 The length of the nano rod is 1-3 mu m, and the average diameter is 30-50nm.
Further, one-dimensional ZnCo 2 O 4 The length of the nanowire is 400-500nm.
Further, the three-dimensional feather-like structure is formed by Co 3 O 4 The nano rod is a framework and ZnCo 2 O 4 The nanowire is formed by a 'wing'.
The preparation method of the capacitance-enhanced three-dimensional feather-shaped zinc cobalt oxide lithium battery anode material comprises the following steps:
step one, co growth on foam Nickel 3 O 4 Nanorod array
1) Cutting foam nickel into blocks, cleaning, oven drying, and adding Co (No 3 ) 2 ·6H 2 O is added into deionized water to prepare Co (No) with the concentration of 0.01 to 0.03nmol/mL 3 ) 2 A solution; to Co (No) 3 ) 2 Adding 3.8-4.2 nmol of NH into the solution 4 F and 5.8 to 6.2nmol of CH 4 N 2 O, continuously stirring until the solution turns pink;
2) Adding pink solution into a reaction kettle, vertically adding washed and dried foam nickel into the reaction kettle, heating for 6 hours at 118-122 ℃, cooling to room temperature, taking out the foam nickel with powder, ultrasonically washing with deionized water and absolute ethyl alcohol for several times, and drying at 60 ℃ to obtain growing Co (OH) 2 Is a nickel foam;
3) Co (OH) 2 Placing the foam nickel into a muffle furnace preheated to 60-80 ℃, heating to 298-302 ℃ at a heating rate of 8-1.2 ℃/min, continuously calcining for 2h, taking out the foam nickel calcined to black after cooling the muffle furnace, standing for 10-15min, respectively ultrasonically cleaning the foam nickel for several times by using deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain the growing Co 3 O 4 Black foam nickel of the nano rod;
step two, in Co 3 O 4 Growth of ZnCo on nanorods 2 O 4 Nanowire
4) Zn (No) 3 ) 2 ·6H 2 O and Co (No) 3 ) 2 ·6H 2 Adding O into deionized water, stirring, adding NH 4 F and CH 4 N 2 O, then continuously stirring to obtain pink solution;
wherein Zn (No) 3 ) 2 ·6H 2 O、Co(No 3 ) 2 ·6H 2 O、NH 4 F and CH 4 N 2 The molar ratio of O is 1:1.8 to 2.2:7.8 to 8.2:11.8 to 12.2;
5) Zn (No) 3 ) 2 ·6H 2 O and Co (No) 3 ) 2 ·6H 2 Pouring O solution into a reaction kettle, and then pouring the Co obtained in the step 3) 3 O 4 The black foam nickel of the nano rod is vertically placed into a reaction kettle; sealing the reaction kettle, putting the reaction kettle into an oven, heating the reaction kettle to 118-122 ℃ by using water, keeping the temperature for 6 hours, cooling the reaction kettle to room temperature, and taking out black foam nickel stained with pink powder; ultrasonic cleaning black foam nickel with deionized water and absolute ethanol for several times, and oven drying at 60deg.C to obtain grown Co 3 O 4 /ZnCo 2 O 4 Black foam nickel in an intermediate state;
6) Will grow Co 3 O 4 /ZnCo 2 O 4 Placing the intermediate black foam nickel in a muffle furnace preheated to 100 ℃, heating to 195-200 ℃ at a heating rate of 0.8-1.2 ℃/min, heating to 295-305 ℃ at a heating rate of 1.8-2.2 ℃/min, continuously calcining for 2 hours, cooling the muffle furnace to room temperature, taking out the black foam nickel, ultrasonically cleaning the black foam nickel with deionized water and absolute ethyl alcohol for several times, and drying at 60 ℃ to obtain the capacitance-enhanced three-dimensional feather-shaped Co growing on the foam nickel 3 O 4 /ZnCo 2 O 4 。
The invention uses the foam nickel as the growth substrate of the composite material, thereby reducing the difficulty and time for assembling the battery.
The foam nickel is vertically placed in a reaction kettle, so that the composite material can be ensured to uniformly grow on the foam nickel.
Further, in step 3) and step 6), the muffle furnace is preheated to 60-80 ℃.
Further, the Co (No 3 ) 2 ·6H 2 O、NH 4 F and CH 4 N 2 The molar ratio of O is 1:4:6.
further, the Co to be grown 3 O 4 /ZnCo 2 O 4 Placing the intermediate black foam nickel into a muffle furnace preheated to 100 ℃, heating to 200 ℃ at a heating rate of 0.8-1.0 ℃/min, heating to 295-300 ℃ at a heating rate of 1.8-2.0 ℃/min, and continuously performingCalcination for 2 h.
Further, the Zn (No 3 ) 2 ·6H 2 O、Co(No 3 ) 2 ·6H 2 O、NH 4 F and CH 4 N 2 The molar ratio of O is 1:2:8:12.
three-dimensional feather Co of the invention 3 O 4 /ZnCo 2 O 4 the/NF is composed of one-dimensional Co 3 O 4 Nanorods and one-dimensional ZnCo 2 O 4 The nanowire is formed by combining; one-dimensional Co 3 O 4 The nanorods consist of an arrangement of nanocrystalline grains with an average diameter of 28-32nm, co 3 O 4 The length of the nano rod is 1-3 mu m, and the average diameter is 30-50nm; co can be seen from SEM images 3 O 4 The surface of the nano rod is smooth, which indicates that the nano rod grows completely in the hydrothermal process; znCo 2 O 4 The nanowire length is 400-500nm, and ZnCo can be found by SEM and TEM images 2 O 4 Uniformly grow on Co 3 O 4 Around the nanorods, thus in Co 3 O 4 The nano rod is a framework and ZnCo 2 O 4 The nanowire is a wing to form a three-dimensional feather-like structure; three-dimensional feather-like structure Co 3 O 4 /ZnCo 2 O 4 Uniformly and tightly grow on foam nickel, znCo 2 O 4 The nano wire is well supplemented with Co 3 O 4 The gaps among the nano rods have more electrochemical active substances in a unit volume, so that the three-dimensional feather-like structure has more electrochemical reaction area and more reaction sites; in addition, co 3 O 4 The nano rods are contacted with each other to form a top cross-linked structure, znCo 2 O 4 The nanowires are closely connected with each other, so that the moving distance in the process of lithium ion transmission is reduced, and the aggregation and release of lithium ions are accelerated.
After one-time hydrothermal treatment, co is adopted in the three-dimensional feather-shaped structure 3 O 4 The nano grass grows, the larger specific surface area after secondary hydrothermal treatment is Co with single component compared with that of primary hydrothermal treatment 3 O 4 Or ZnCo 2 O 4 . Feather shapeThe tops of the structures are mutually connected, so that the transmission distance of lithium ions is shortened, the aggregation and release of lithium ions are accelerated, and the acceleration effect is considered to be peculiar to a three-dimensional feather shape. With ZnCo 2 O 4 Compounding is not the most recent research effort, but the three-dimensional feathered structure is characteristic. The three-dimensional feather-like influence is the largest capacitance characteristic ratio (81.25%), and the large capacitance characteristic ratio can enhance the charging and discharging capacity and the cycling stability of the battery under high current.
The invention has the following beneficial effects:
co prepared by the invention 3 O 4 /ZnCo 2 O 4 The NF is a composite nano array material growing on the foam nickel, and Co is firstly grown on the foam nickel by a secondary hydrothermal method 3 O 4 Nanorods and then at Co 3 O 4 Growth of ZnCo on nanorods 2 O 4 Nanowires with Co 3 O 4 Is a 'skeleton', znCo 2 O 4 A feather-like structure is formed for the 'wings'. The three-dimensional feather-shaped Co is reduced by pre-heating and variable-temperature calcination process treatment in the hydrothermal and calcination processes 3 O 4 /ZnCo 2 O 4 The time required for/NF improves the yield of the composite sample.
Due to Co in the first hydrothermal process 3 O 4 The nanorods uniformly and tightly grow on the foam nickel skeleton and occupy all growth sites on the foam nickel, thus leading to ZnCo in the second hydrothermal process 2 O 4 Nanowires can only be used in Co 3 O 4 The nanorods start to grow on the nano-rods, so that a three-dimensional feather-like structure is formed. ZnCo 2 O 4 The nano wire is well supplemented with Co 3 O 4 The spaces between the nanorods, the additional nanowires increase the specific surface area of the material and the electrochemical reaction sites compared to other non-tightly-interwoven structures such as nanoplatelets or nanofiber structures. As shown in fig. 8, lithium ions can pass ZnCo interwoven together 2 O 4 The nanowires are transported, which reduces the transport distance of lithium ions, thus increasing the transport efficiency of lithium ions, which is a closely arranged three-dimensional plumeThe lithium ions are thus rapidly accumulated and released, which is peculiar to the wool structure, so that Co 3 O 4 /ZnCo 2 O 4 Exhibit a large capacitance characteristic contribution ratio (more than 80%), which also further enhances Co 3 O 4 /ZnCo 2 O 4 Is used for the electrochemical performance of the battery. Through physical characterization test and electrochemical test, three-dimensional feather-like Co 3 O 4 /ZnCo 2 O 4 NF and one-dimensional nano grass-like Co 3 O 4 The specific surface area is larger than that of the NF (65 m 2 ·g -1 Ratio of 51m 2 ·g -1 ) The initial discharge capacity is larger (1480 mAh.g) -1 Ratio 1203 mAh.g -1 ) The cycle life is better (934 mAh.g after 200 charge and discharge cycles) -1 Ratio 564mAh g -1 ) Has more excellent rate performance (786 mAh.g) -1 Ratio 449 mAh.g -1 ) The capacitance characteristic is larger (81.25% to 46.15%). Specific surface area compared to Co alone 3 O 4 Larger.
Compared with Co with other morphologies 3 O 4 /ZnCo 2 O 4 There are significant advantages in cycle life and capacitance characteristics.
Co 3 O 4 And ZnCo 2 O 4 Is synergistic in that the capacitance is enhanced Co 3 O 4 /ZnCo 2 O 4 Electrochemical performance of/NF is superior to single Co 3 O 4 Or ZnCo 2 O 4 . Three-dimensional feather-like Co as negative electrode material of lithium ion battery 3 O 4 /ZnCo 2 O 4 The capacity of/NF is larger (the initial discharge capacity is far beyond that of graphite materials), the stability (compared with the common graphite anode materials) is better, and the production process is environment-friendly and safe. The larger capacitance characteristic ratio ensures that the quick charge and discharge capacity of the lithium ion battery is better than that of a common lithium ion battery, and the lithium ion battery is a cathode material of a high-performance lithium ion battery which has potential to replace graphite materials.
Drawings
FIG. 1 is (a-c) Co 3 O 4 Low-magnification and high-magnification SEM images of/NF nanorod arrays and (d-f) capacitance-enhanced Co 3 O 4 /ZnCo 2 O 4 Low-magnification and high-magnification SEM images of NF nanoarrays;
FIG. 2 is Co 3 O 4 TEM image (a) and HRTEM image (b-c) of NF nanorods, and three-dimensional feathered Co 3 O 4 /ZnCo 2 O 4 TEM image (d) and HRTEM image (e-f) of/NF;
FIG. 3 is (a) Co 3 O 4 /ZnCo 2 O 4 /NF; (b) Zn 2p; XPS spectra of (c) Co 2p and (d) O1 s;
FIG. 4 is (a) Co 3 O 4 NF and (b) Co 3 O 4 /ZnCo 2 O 4 Nitrogen isothermal adsorption and desorption curve and pore size distribution curve of/NF;
FIG. 5 is (a) Co 3 O 4 NF and (b) Co 3 O 4 /ZnCo 2 O 4 a/NF charge-discharge graph;
FIG. 6 is Co 3 O 4 NF and Co 3 O 4 /ZnCo 2 O 4 a/NF rate performance plot;
FIG. 7Co 3 O 4 NF and Co 3 O 4 /ZnCo 2 O 4 Capacitance characteristic ratio map of/NF;
FIG. 8 is Li + Schematic of insertion/extraction.
Detailed Description
For the purposes of clarity, technical solutions and advantages of embodiments of the present invention, the spirit of the present disclosure will be described in detail below, and any person skilled in the art, after having appreciated the embodiments of the present disclosure, may make changes and modifications to the techniques taught by the present disclosure without departing from the spirit and scope of the present disclosure.
The exemplary embodiments of the present invention and the descriptions thereof are intended to illustrate the present invention, but not to limit the present invention.
Example 1
Capacitance-enhanced Co of the present embodiment 3 O 4 /ZnCo 2 O 4 The preparation method of the/NF lithium battery anode material comprises the following steps:
step one, growing on foam nickelCo 3 O 4 Nanorod array
1) The nickel foam was cut into 3cm x 3cm squares and each was ultrasonically cleaned with deionized water and ethanol for 10 minutes to adequately remove impurities from the nickel foam. Drying the foam nickel at 60 ℃ and then placing the foam nickel for standby. Weigh 1nmol of Co (No 3 ) 2 ·6H 2 O was added to 50mL of deionized water to prepare Co (No) having a concentration of 0.02nmol/mL 3 ) 2 A solution; weigh 4nmolNH 4 F and 6nmolCH 4 N 2 O was added as a precipitant to Co (No 3 ) 2 Placing the prepared solution into a magnetic stirrer to stir for about 10 minutes until the solution turns into uniform pink;
2) Pink Co (No 3 ) 2 Pouring the solution into a 60mL reaction kettle, and vertically placing the cleaned foam nickel into the reaction kettle to ensure Co 3 O 4 The nanorods grow uniformly. Sealing the reaction kettle, putting the reaction kettle into an oven, carrying out hydrothermal treatment at 120 ℃ for 6 hours, taking out the reaction kettle after the temperature is reduced, standing for 10-15 minutes, opening the reaction kettle, taking out foam nickel stained with pink powder, respectively carrying out ultrasonic cleaning on the foam nickel by deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain growing Co (OH) 2 Is a nickel foam;
3) Will grow Co (OH) 2 The foamed nickel is put into a muffle furnace preheated to 60-80 ℃, the heating rate of the muffle furnace is set to be 1 ℃/min, and the heating is stopped and the calcination is continued for 2 hours after the temperature in the muffle furnace reaches 300 ℃. Taking out the foam nickel calcined to black after cooling the muffle furnace, standing for 10-15 minutes, respectively cleaning the foam nickel by deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain the grown Co 3 O 4 Black foam nickel of the nanorods.
Step two, in Co 3 O 4 Growth of ZnCo on nanorods 2 O 4 Nanowire
4) Weigh 1nmol Zn (No) 3 ) 2 ·6H 2 O and 2nmol Co (No 3 ) 2 ·6H 2 O is poured into 50mL of deionized water in sequence, and 8nmol of NH is added 4 F and 12nmol CH 4 N 2 O is used as a precipitator, and the prepared solution is placed on a magnetic stirrer to be stirred for 10-15 minutes until the solution shows even pink;
5) Zn (No) 3 ) 2 ·6H 2 O and Co (No) 3 ) 2 ·6H 2 Pouring the O solution into a 60mL reaction kettle, and vertically placing the cleaned black foam nickel into the reaction kettle to ensure ZnCo 2 O 4 The nanowires are grown uniformly. And (3) sealing the reaction kettle, putting the reaction kettle into an oven, heating the reaction kettle to 120 ℃ in the oven, continuously performing hydrothermal treatment for 6 hours, taking out the sealed reaction kettle after the temperature in the oven is reduced, standing the reaction kettle for 10-15min, opening the reaction kettle, and taking out the black foam nickel stained with pink powder. Ultrasonic cleaning black foam nickel with deionized water and absolute ethanol for several times, and oven drying at 60deg.C to obtain grown Co 3 O 4 /ZnCo 2 O 4 The black foam nickel in the intermediate state,
6) Will grow Co 3 O 4 /ZnCo 2 O 4 Intermediate black foam nickel (herein black foam nickel means attached Co 3 O 4 /ZnCo 2 O 4 Intermediate nickel foam) was placed in a muffle furnace preheated to 100 c, heated to 200 c at a heating rate of 1 c/min, and heated to 300 c at a heating rate of 2 c/min for 2 hours. Taking out the black foam nickel after cooling the muffle furnace to room temperature, standing the black foam nickel for 10-15min, respectively carrying out ultrasonic cleaning on the black foam nickel by deionized water and absolute ethyl alcohol, and drying the foam nickel at 60 ℃ to obtain the capacitance-enhanced three-dimensional feather-shaped Co growing on the foam nickel 3 O 4 /ZnCo 2 O 4 The specific surface area is 63-66 m 2 g -1 The porosity is 30% -40%.
FIG. 1 shows the (a-c) Co of the present embodiment 3 O 4 Low-magnification and high-magnification SEM images of/NF nanorod arrays and (d-f) capacitance-enhanced Co 3 O 4 /ZnCo 2 O 4 Low-magnification and high-magnification SEM images of NF nanoarrays; wherein a, b and c are Co 3 O 4 SEM image of/NF, d,e. f is Co 3 O 4 /ZnCo 2 O 4 SEM image of/NF. It can be seen that Co grows on the nickel foam after the first calcination 3 O 4 Nanorods, after secondary calcination, co 3 O 4 Growth of ZnCo on nanorods 2 O 4 The nanowire takes the nanorod as a framework, and the nanowire and the nanorod form a three-dimensional feather-shaped structure.
FIG. 2 shows Co of the present embodiment 3 O 4 TEM image (a) and HRTEM image (b-c) of NF nanorods, and three-dimensional feathered Co 3 O 4 /ZnCo 2 O 4 TEM image (d) and HRTEM image (e-f) of/NF; in the figure, a is Co 3 O 4 TEM image of/NF, b, c are HRTEM images; d is Co 3 O 4 /ZnCo 2 O 4 TEM image of/NF, e and f are HRTEM images. Co can be seen 3 O 4 The nanorod consists of nano crystal grains and feather Co 3 O 4 /ZnCo 2 O 4 Consists of solid nanorods and surrounding nanowires. The HRTEM lattice stripes of the two materials are clear, which shows that the composite material has good crystallinity.
Fig. 3 is a total energy spectrum of the present example, showing that the sample contains Zn, ni, co, O and C elements, without other impurities. The energy spectra of Zn, co and O elements are shown in the figures (b-d). Through Gaussian fitting analysis, the Zn 2p spectrogram shows two main peaks at 1023.4eV and 1044.5eV, which correspond to Zn3/2 and Zn1/2 respectively. The Co 2p spectrum shows four main peaks at 797.5eV,781.3eV,780.1eV and 795.6 eV. Wherein 797.5eV and 781.3eV correspond to Co 2p 1/2 780.1eV and 795.6eV correspond to Co 2p 3/2 Indicating the presence of Co 2+ And Co 3+ . There are also two satellite peaks 786.3eV and 804.1eV (labeled "sat"), respectively. The O2 p spectrum shows three main peaks at 529.6eV,531.3eV and 531.9 eV. Wherein an O1 fitted peak at 529.6eV indicates the presence of a metal-oxygen bond, i.e. Zn-Co-O or Co-O. In conclusion, zn exists in the material 2+ ，Zn 3+ ，Co 2+ ，Co 3+ And O 2- Indicating successful Co recombination on NF 3 O 4 /ZnCo 2 O 4 。
FIG. 4 shows Co of the present embodiment 3 O 4 NF and Co 3 O 4 /ZnCo 2 O 4 BET image of/NF, according to the image, the specific surface area of two materials can be obtained, which are respectively 51m 2 g -1 And 65m 2 g -1 The specific surface area after compounding is obviously increased, and the larger specific surface area brings larger electrochemical reaction area and more electrochemical reaction sites. In addition, co 3 O 4 /ZnCo 2 O 4 The pore size distribution of/NF is more compact and uniform, and is concentrated in the size of 10 nm.
FIG. 5 is Co of the present embodiment 3 O 4 NF and Co 3 O 4 /ZnCo 2 O 4 Charge-discharge cycle image of/NF, co can be obtained 3 O 4 /ZnCo 2 O 4 The discharge specific capacity of/NF is larger, and the residual capacity after 5 charge-discharge cycles is also more, which shows that the stability of the composite material is obviously enhanced.
FIG. 6 is Co of the present embodiment 3 O 4 NF and Co 3 O 4 /ZnCo 2 O 4 A magnification image of/NF, it can be observed that the discharge capacity gradually decays as the current density increases, returning to 0.2Ag as the current density returns -1 When Co 3 O 4 /ZnCo 2 O 4 The discharge capacity of/NF was returned to substantially the most initial level, approximately 92.8% of the initial, far beyond Co 3 O 4 and/NF, the composite material has better stability under the condition of large current and excellent charge and discharge characteristics.
FIG. 7 is Co of the present embodiment 3 O 4 NF and Co 3 O 4 /ZnCo 2 O 4 A resistive-capacitive characteristic profile of/NF, co can be obtained by observing the image 3 O 4 /ZnCo 2 O 4 The capacitance characteristic of the/NF is obviously enhanced, compared with Co 3 O 4 the/NF was about 35% more. The large capacitance characteristic shows that the battery has more excellent performance in high-current charge and discharge.
FIG. 8 shows a three-dimensional feathered Co of the present embodiment 3 O 4 /ZnCo 2 O 4 /NF (nff)Lithium ion intercalation/extraction process. After the first discharge period, li + With Co 3 O 4 /ZnCo 2 O 4 Some complex irreversible reactions occur to form nano-dispersed Co and Zn metal particles, liZn alloys and Li 2 O. At the same time, this irreversible reaction leads to ZnCo 2 O 4 Generates some extra Li 2 O. In a subsequent reaction, co and Zn metal particles are combined with additional Li 2 O reacts to generate Li+ to greatly improve Co 3 O 4 /ZnCo 2 O 4 Is a reversible capacity of (a). In addition, the alloy reaction between Zn and Li also contributes to the improvement of the partially reversible capacity. On the other hand, dispersed Co and Zn metal particles can improve the conductivity of the material, thereby improving the cycle and rate performance thereof.
Example 2
Core-shell Co of the present example 3 O 4 /ZnCo 2 O 4 The preparation method of the hollow sphere lithium battery anode material is different from that of the embodiment 1:
1. the precipitant in step 1) is Co (NO) 3 ) 2 ·6H 2 O、C 6 H 5 Na 3 O 7 ·2H 2 O and C 6 H 12 N 4 ；
2. Step 2) hydrothermal treatment is carried out for 24 hours at the hydrothermal temperature of 100 ℃ to prepare the Co in the shape of growing nuclear shell 3 O 4 Intermediate nickel foam;
3. calcining at 200 ℃ for 3 hours in the step 3) to obtain the growing core-shell Co 3 O 4 Black foam nickel of the hollow sphere;
4. in the step 5), the hydrothermal reaction is eliminated, and the vacuum drying is carried out for 12 hours at the temperature of 60 ℃ to prepare the growing intermediate state core-shell Co 3 O 4 /ZnCo 2 O 4 Black foam nickel of the hollow sphere;
5. calcining at 400 ℃ for 3 hours in the step 6) to prepare the growing core-shell Co 3 O 4 /ZnCo 2 O 4 A hollow sphere.
Otherwise, the same as in example 1 was used.
Capacitance enhanced three-dimensional feather-like Co prepared in example 1 3 O 4 /ZnCo 2 O 4 . Capacitor enhanced core-shell Co prepared in example 2 3 O 4 /ZnCo 2 O 4 . Compared with the prior ZnCo 2 O 4 /Co 3 O 4 The performance of/CC and graphite negative electrode is compared as follows.
From the comparison of the performances of the above tables, it can be known that the three-dimensional feathered Co after compounding 3 O 4 /ZnCo 2 O 4 The method has certain advantages in all aspects of electrochemical performance compared with similar materials with other morphologies prepared by the prior art. The reversible capacity is increased due to feathered Co 3 O 4 /ZnCo 2 O 4 The electrochemical reaction active substances are more in unit volume than the materials such as hollow core-shell and the like, so the porous nickel foam has larger reversible capacity. From SEM images, co 3 O 4 Nanorods are slightly curved, interwoven, and ZnCo 2 O 4 The nanowire forms a three-dimensional feather array, and the structure effectively inhibits the agglomeration effect in the circulation process, so that the nanowire has good circulation stability. ZnCo 2 O 4 The nanowires form a top cross-linked structure, so that lithium ions can be rapidly gathered and released, and therefore, the nanowires have larger capacitance characteristic occupation ratio and good multiplying power performance.

Claims (10)

1. A capacitance-enhanced three-dimensional feather-shaped zinc cobalt oxide lithium battery anode material is characterized in that the lithium battery anode material is prepared from Co 3 O 4 And ZnCo 2 O 4 Is prepared by the method;
the lithium battery anode material is of a three-dimensional feather-like structure, and the specific surface area is 63-66 m 2 ·g -1 The porosity is 30% -40%.
2. The capacitance-enhanced three-dimensional feather-shaped zinc cobalt oxide lithium battery anode material according to claim 1, wherein the three-dimensional feather-shaped structure is Co 3 O 4 /ZnCo 2 O 4 the/NF is made of one-dimensional Co 3 O 4 Nanorods and one-dimensional ZnCo 2 O 4 The nanowire is assembled.
3. The capacitance-enhanced three-dimensional feather-like zinc cobalt oxide lithium battery anode material according to claim 2, wherein the one-dimensional Co is characterized in that 3 O 4 The nanorods consist of an arrangement of nanocrystalline grains with diameters of 28-32nm, co 3 O 4 The length of the nano rod is 1-3 mu m, and the average diameter is 30-50nm.
4. The capacitance-enhanced three-dimensional feather-like zinc cobalt oxide lithium battery anode material according to claim 2, wherein the one-dimensional ZnCo is characterized in that 2 O 4 The length of the nanowire is 400-500nm.
5. A capacitance enhanced three-dimensional feather-like zinc cobalt oxide lithium battery anode material according to any one of claims 1 to 4, wherein said three-dimensional feather-like structure is formed by Co 3 O 4 The nano rod is a framework and ZnCo 2 O 4 The nanowire is formed by a 'wing'.
6. A method for preparing the capacitance-enhanced three-dimensional feather-like zinc cobalt oxide lithium battery anode material as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps:
step one, co growth on foam Nickel 3 O 4 Nanorod array
1) Cutting foam nickel into blocks, cleaning, oven drying, and adding Co (No 3 ) 2 ·6H 2 O is added into deionized water to prepare Co (No) with the concentration of 0.01 to 0.03nmol/mL 3 ) 2 A solution; to Co (No) 3 ) 2 Adding N into the solutionH 4 F and CH 4 N 2 O, continuously stirring until the solution turns pink;
wherein Co (No 3 ) 2 ·6H 2 O、NH 4 F and CH 4 N 2 The molar ratio of O is 1:3.8 to 4.2:5.8 to 6.2;
2) Adding pink solution into a reaction kettle, vertically adding washed and dried foam nickel into the reaction kettle, heating for 6 hours at 118-122 ℃, cooling to room temperature, taking out the foam nickel with powder, ultrasonically washing with deionized water and absolute ethyl alcohol for several times, and drying at 60 ℃ to obtain growing Co (OH) 2 Is a nickel foam;
3) Co (OH) 2 Placing the foam nickel into a muffle furnace, heating to 298-302 ℃ at a heating rate of 0.8-1.2 ℃/min, continuously calcining for 2h, taking out the foam nickel calcined to black after the muffle furnace is cooled, standing for 10-15min, respectively ultrasonically cleaning the foam nickel for several times by deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain the growing Co 3 O 4 Black foam nickel of the nano rod;
step two, in Co 3 O 4 Growth of ZnCo on nanorods 2 O 4 Nanowire
4) Zn (No) 3 ) 2 ·6H 2 O and Co (No) 3 ) 2 ·6H 2 Adding O into deionized water, stirring, adding NH 4 F and CH 4 N 2 O, then continuously stirring to obtain pink solution;
wherein Zn (No) 3 ) 2 ·6H 2 O、Co(No 3 ) 2 ·6H 2 O、NH 4 F and CH 4 N 2 The molar ratio of O is 1:1.8 to 2.2:7.8 to 8.2:11.8 to 12.2;
5) Zn (No) 3 ) 2 ·6H 2 O and Co (No) 3 ) 2 ·6H 2 Pouring O solution into a reaction kettle, and then pouring the Co obtained in the step 3) 3 O 4 The black foam nickel of the nano rod is vertically placed into a reaction kettle; heating to 118-122 deg.C, maintaining for 6 hr, cooling to room temperature, and collecting pink powderBlack foam nickel; ultrasonic cleaning black foam nickel with deionized water and absolute ethanol for several times, and oven drying at 60deg.C to obtain grown Co 3 O 4 /ZnCo 2 O 4 Black foam nickel in an intermediate state;
6) Will grow Co 3 O 4 /ZnCo 2 O 4 Placing the intermediate black foam nickel in a muffle furnace preheated to 100 ℃, heating to 195-200 ℃ at a heating rate of 0.8-1.2 ℃/min, heating to 295-305 ℃ at a heating rate of 1.8-2.2 ℃/min, continuously calcining for 2 hours, cooling the muffle furnace to room temperature, taking out the black foam nickel, ultrasonically cleaning the black foam nickel with deionized water and absolute ethyl alcohol for several times, and drying at 60 ℃ to obtain the capacitance-enhanced three-dimensional feather-shaped Co growing on the foam nickel 3 O 4 /ZnCo 2 O 4 An electrical negative electrode material.
7. The preparation method of the capacitance enhanced three-dimensional feather-shaped zinc cobalt oxide lithium battery anode material is characterized in that in step 6) in step 3), a muffle furnace is preheated to 60-80 ℃.
8. The method for preparing a capacitor-enhanced three-dimensional feather-like zinc cobalt oxide lithium battery anode material according to claim 6, wherein the Co (No 3 ) 2 ·6H 2 O、NH 4 F and CH 4 N 2 The molar ratio of O is 1:4:6.
9. the method for preparing a capacitance enhanced three-dimensional feather-like zinc cobalt oxide lithium battery anode material according to claim 6, wherein Co is grown 3 O 4 /ZnCo 2 O 4 The intermediate black foam nickel is placed in a muffle furnace preheated to 100 ℃, heated to 200 ℃ at a heating rate of 0.8-1.2 ℃/min, heated to 295-305 ℃ at a heating rate of 1.8-2.2 ℃/min, and then continuously calcined for 2 hours.
10. According to claim 6Is characterized in that the Zn (No 3 ) 2 ·6H 2 O、Co(No 3 ) 2 ·6H 2 O、NH 4 F and CH 4 N 2 The molar ratio of O is 1:2:8:12.
CN202310866873.XA 2023-07-14 2023-07-14 Capacitance-enhanced three-dimensional feather-shaped zinc cobalt oxide lithium battery anode material and preparation method thereof Pending CN116960296A (en)

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