CN109378458B - Preparation of sodium ion battery negative electrode material ZnS/C-SnO by using tin mud2Method (2) - Google Patents

Preparation of sodium ion battery negative electrode material ZnS/C-SnO by using tin mud2Method (2) Download PDF

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CN109378458B
CN109378458B CN201811228765.5A CN201811228765A CN109378458B CN 109378458 B CN109378458 B CN 109378458B CN 201811228765 A CN201811228765 A CN 201811228765A CN 109378458 B CN109378458 B CN 109378458B
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李建中
王颖
骆文彬
李犁
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Northeastern University China
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Abstract

The invention relates to a method for preparing a cathode material ZnS/C-SnO of a sodium ion battery by using stannic mud2The method of (1), comprising: s1: washing and drying the tin mud to obtain SnO2A material; s2: carrying out hydrothermal reaction on zinc salt, a sulfur source and an organic carbon source serving as raw materials, collecting precipitates and drying after the reaction is finished to obtain a composite material precursor, and roasting the composite material precursor in an inert atmosphere to obtain the ZnS/C composite material; s3 SnO prepared in the step S12The material is mixed with the ZnS/C composite material prepared in the step S2 in proportion to prepare the ZnS/C-SnO negative electrode material of the sodium-ion battery2. The invention solves the problem that the tin mud generated in the tin plating process is not properly recycled, and the preparation of the sodium ion battery cathode material by adopting the tin mud solves the problem of SnO2The cost is high, the cost of the raw materials is effectively reduced, the concept of low cost of the sodium ion battery is better met, and the comprehensive utilization of resources is realized.

Description

Preparation of sodium ion battery negative electrode material ZnS/C-SnO by using tin mud2Method (2)
Technical Field
The invention relates to the technical field of battery materials, in particular to a method for preparing a cathode material ZnS/C-SnO of a sodium ion battery by using stannic mud2The method of (1).
Background
Secondary batteries occupy a very important position in the field of new energy as an important technology for energy storage and conversion. In order to deal with the energy crisis, the development of the secondary battery which is efficient, convenient and suitable for large-scale energy storage has very important significance. Because lithium resources are scarce, the price of lithium salt is continuously increased and is high, which seriously restricts the continuous development of the lithium ion battery in the field of energy storage. In contrast, sodium has similar chemical properties to lithium and is extremely abundant, which makes sodium-ion batteries far less expensive than lithium-ion batteries. Therefore, sodium ion batteries are expected to replace lithium ion batteries in energy storage systems.
The negative electrode material of the sodium-ion battery is responsible for providing low oxidation-reduction potential and has high requirements on safety and effectiveness. In the related research of the cathode material of the sodium-ion battery at present, the main cathode material comprises metal oxide and carbon material, but most of the metal oxide has high manufacturing cost, is not consistent with the low-cost concept of the sodium-ion battery, and the initial capacity of the cathode material is not high, so that the cycle performance is not ideal. Tin oxide has attracted much attention because of its high specific capacity and good conductivity, and it has ideal cycle stability as a negative electrode material for sodium ion batteries. Tin oxide and sodium ion can undergo conversion reaction, SnO2Has higher theoretical capacity. The first sodium insertion of Sn mainly comprises two processes: first form NaxSn (x-0.5) alloy, and further react to form Na15Sn4(x ═ 3.75), a volume expansion of 420% was achieved, but the huge volume expansion did not cause collapse and fragmentation of the material, and the structure of the material remained essentially intact. This important finding suggests that Sn theoretically achieves good cycling stability as a sodium ion battery negative electrode material, but SnO2The price is very expensive, which limits the commercialization process.
In the plating solution of the conventional tin plating process, Sn is generated2+Oxidation of electron lost to Sn in the anode region4+Thereby producing tin sludge. The generation of tin sludge leads to Sn in the plating solution2+Increases the consumption of the tin anode, thereby resulting in higher production costs. The production of tin sludge represents an economic loss, and the discharge of tin sludge necessarily aggravates the environmental pollution. The prior art is not ideal for treating the tin sludge and cannot be recycled properly. Meanwhile, the production process flow of tin oxide is very complicated, so that commercial SnO is caused2Is very expensive.
In view of the above problems, an object of the present invention is to provide a method for producing a negative electrode material for a sodium ion battery, which can recycle tin sludge properly and at low cost.
Disclosure of Invention
Technical problem to be solved
In order to solve the problems in the prior art, the invention provides a method for preparing a cathode material ZnS/C-SnO of a sodium-ion battery by using tin mud2The method comprises the steps of firstly obtaining SnO through tin mud2Then the obtained product is used for preparing a negative electrode material ZnS/C-SnO of the sodium-ion battery2On one hand, Sn in the tin mud is recycled, the environmental pollution is reduced, on the other hand, the battery cathode material with good performance is prepared at lower cost, and the comprehensive utilization of resources is realized.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
preparation of sodium ion battery negative electrode material ZnS/C-SnO by using tin mud2The method of (1), comprising:
s1: washing and drying the tin mud to obtain SnO2A material;
s2: carrying out hydrothermal reaction on zinc salt, a sulfur source and an organic carbon source serving as raw materials, collecting precipitates and drying after the reaction is finished to obtain a composite material precursor, and roasting the composite material precursor in an inert atmosphere to obtain the ZnS/C composite material;
s3 SnO prepared in the step S12The material is mixed with the ZnS/C composite material prepared in the step S2 in proportion to prepare the ZnS/C-SnO negative electrode material of the sodium-ion battery2。
The steps S1 and S2 have no sequence, or the sequence is interchangeable.
Preferably, the washing of the tin sludge in step S1 includes: washing with distilled water and absolute ethyl alcohol; and during washing, the volume ratio of the mixed tin mud and distilled water or absolute ethyl alcohol is 1-5: 6.
Washing with distilled water can remove SO in tin mud3And other water-soluble acids or salts in minor amounts; while the absolute ethyl alcohol washing can almost remove all mixed tin mudAnd (4) machines and objects.
Preferably, in step S1, the washing includes more than 3 times, that is, more than 3 times of washing with distilled water and more than 3 times of washing with anhydrous ethanol, and the washing with distilled water and the washing with anhydrous ethanol are sequentially performed or alternately performed.
Preferably, the drying in step S1 is drying at 60-80 deg.C for 10-12h to obtain light yellow green powder, i.e. SnO2A material.
SnO prepared by washing and drying2SnO in material2The purity of (A) is 95% or more, and a trace amount of silicon oxide and insoluble metal oxides such as iron oxide, aluminum oxide, bismuth oxide and the like are contained. The oxide impurities do not need to be removed intentionally, the content of the oxide impurities is moderate, the oxide impurities can be used for doping the negative electrode material of the sodium-ion battery, and the battery cycling stability of the battery material can be further improved through the doping effect. In other words, it is due to the high content of SnO in the tin sludge2And the oxide impurities which are slightly contained are all suitable for manufacturing the cathode material of the sodium-ion battery, so the method for treating the tin mud not only simplifies the recovery process of the tin mud, but also realizes high-value comprehensive utilization.
Preferably, in step S2, the zinc salt is one or more of zinc acetate, zinc nitrate, and zinc chloride; the sulfur source is one or more of sulfur powder, sodium sulfide and thiourea; the organic carbon source is one or more of glucose, sucrose, starch and citric acid; and the zinc salt, the sulfur source and the organic carbon source are dissolved in water and then transferred to a hydrothermal reaction kettle for sealing reaction.
Preferably, in the step S2, the temperature of the hydrothermal reaction is 120 to 180 ℃, and the reaction time is 10 to 14 hours.
Preferably, in step S2, after the hydrothermal reaction is finished, the precipitate is collected, and then the hydrothermal reaction product is subjected to centrifugation-washing-ultrasonic dispersion-drying treatment, so as to obtain the composite material precursor. Wherein, the precipitate of the hydrothermal reaction is obtained by centrifugal separation, the washing is carried out for more than 3 times by respectively adopting distilled water and absolute ethyl alcohol, the ultrasonic dispersion is carried out by loading ultrasonic waves in the washing process so as to increase the washing effect (removing impurity ions) and improve the uniformity of the precipitate, and finally, the washed precipitate is dried at 60-80 ℃ for 10-12 h.
In the step S2, the composite material precursor is placed in a nitrogen or argon atmosphere and roasted at 600-900 ℃ for 2-5 h to obtain the ZnS/C composite material.
Preferably, in step S3: SnO prepared from S1 by adopting dry ball milling mode2The material is mixed with a ZnS/C composite material prepared from S2 according to a mass ratio of 1: 1-4, ball milling is carried out for 1-15 h at a ball-to-material ratio of 20-30: 1 and 200-800 r/min, and a negative electrode material ZnS/C-SnO of the sodium ion battery is prepared2。
(III) advantageous effects
The invention has the beneficial effects that:
(1) aiming at the problem that tin sludge generated in a tin plating process is not properly recycled, the invention uses the tin sludge to prepare the sodium ion battery cathode material, and realizes comprehensive high-value recycling of resources.
The tin mud contains about 86.7 percent of SnO29-9.4% of sulfur trioxide, a small amount of organic additives used in the tin plating process, and the balance of water, iron oxide, silicon oxide, bismuth oxide, aluminum oxide and the like accounting for about 1%, so that the main component of the tin mud is SnO2. The invention uses the tin mud as the raw material of the cathode material of the sodium ion battery, only the impurities such as sulfur trioxide, organic additives (mainly phenol sulfonate and aryl compounds) and the like are needed to be removed, the C, O, S element content is reduced after washing treatment, the purity of the Sn element is increased, after washing, the components in the original electroplating solution contained in the tin mud are dissolved in the washing solution, and the SnO with the purity of about 95 percent can be obtained2And trace oxides such as iron oxide, silicon oxide, bismuth oxide, aluminum oxide and the like, which do not affect the electrochemical performance of the negative electrode material of the sodium-ion battery, and can play a role in doping to further improve the initial capacity of the battery material and the cycling stability of the battery. Therefore, the invention realizes the recovery of the tin mud by a simpler process, and prepares the battery cathode material with good performance at lower cost.
(2) The invention can be used for recycling the tin mud only by washing and drying. The operation process is very simple, the operation and equipment cost of the recovery process is low, and the economic loss caused by the generation of tin mud in the tin plating process is greatly reduced.
(3) In the invention, the tin mud is SnO2The source of the SnO is solved2The cost is high, the cost of the raw materials is effectively reduced, the concept of low cost of the sodium ion battery is better met, and the comprehensive utilization of resources is realized.
(4) The negative electrode material ZnS/C-SnO of the sodium ion battery prepared by the method2Has better specific capacity and SnO2The electrode material has good stability, meets the performance requirements of the cathode material of the sodium-ion battery, namely has higher initial capacity and ideal cycle stability.
(5) The ZnS/C composite material is obtained by a one-step hydrothermal method, the technological process is simple, and the operation conditions are mild. The ZnS/C-SnO with excellent performance can be prepared by a mechanical ball milling method2The composite material has simple process and can be produced commercially.
The invention takes the by-product tin mud of the tin plating process as the raw material, and provides a preparation method of the cathode material of the sodium ion battery aiming at the problems of low initial capacity, poor cycling stability, high manufacturing cost and the like of the metal oxide cathode material2The defect of high cost is realized, the comprehensive utilization of resources is realized, and a new recycling idea is provided for the tin sludge generated in the tin plating process.
Drawings
FIG. 1 shows ZnS/C-SnO as a product of example 12XRD spectrum of composite material.
In FIG. 2, a, b, C, d are ZnS/C-SnO products of example 32SEM images of the composite material at different magnifications.
FIG. 3 a is the product ZnS/C-SnO of example 32Electronic images (reference numerals 91, 92, 93) of the composite material, b, c, d of FIG. 3 beingEDS analysis spectra corresponding to the locations of the marks 91, 92, 93 on the electronic image of a.
Fig. 4 is a table of energy spectrum element analysis corresponding to EDS analysis spectra 91, 92, 93 of fig. 3.
FIG. 5 shows ZnS/C-SnO in example 22And the multiplying power cycle performance and the coulombic efficiency curve tested after the sodium-ion battery cathode made of the composite material is assembled into a battery.
FIG. 6 is ZnS/C-SnO of example 32Composite material 100mA g-1And after the manufactured sodium ion battery cathode is assembled into a battery, the charging and discharging curve is carried out under a constant current.
FIG. 7 is ZnS/C-SnO in example 42And (3) a cycle performance and coulombic efficiency curve tested after the sodium-ion battery cathode made of the composite material is assembled into a battery.
Detailed description of the preferred embodiment
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The basic idea of the invention is that the high-purity SnO containing doped oxides is prepared by using tin mud which is a byproduct of a tin plating process as a raw material and treating the tin mud by a simple process method2The product is used for manufacturing a negative electrode material of the sodium ion battery, and the negative electrode material is used for manufacturing a battery negative electrode, so that the sodium ion battery can obtain excellent charge-discharge specific capacity and ideal cycling stability.
The invention provides a method for preparing a cathode material ZnS/C-SnO of a sodium ion battery by using tin mud2The method of (1), comprising:
s1: washing and drying the tin mud to obtain SnO2A material;
specifically, the washing of the tin sludge includes: washing with distilled water and absolute ethyl alcohol; and the volume ratio of the mixed tin mud and distilled water or absolute ethyl alcohol is about 1-5: 6 during washing. Washing with distilled water can remove SO in tin mud3And other water-soluble acids or salts in minor amounts; and the absolute ethyl alcohol washing can almost remove all organic matters mixed in the tin mud.
The washing comprises more than 3 times, namely more than 3 times of distilled water washing and more than 3 times of absolute ethyl alcohol washing, and the distilled water washing and the absolute ethyl alcohol washing are sequentially carried out or alternately carried out.
Wherein the drying is carried out at 60-80 ℃ for 10-12h to obtain light yellow green powder, namely SnO2A material.
SnO prepared by washing and drying2SnO in material2The purity of (A) is about 95%, and the composition further contains a trace amount of insoluble metal oxides such as silicon oxide, iron oxide, aluminum oxide and bismuth oxide. The oxide impurities are not required to be removed intentionally, because the oxide impurities can be used as doping of the negative electrode material of the sodium-ion battery, and the initial capacity of the battery material and the battery cycling stability can be further improved through the doping. In other words, it is due to the high content of SnO in the tin sludge2And the oxide impurities which are slightly contained are all suitable for manufacturing the cathode material of the sodium-ion battery, so the method for treating the tin mud not only simplifies the recovery process of the tin mud, but also realizes high-value comprehensive utilization.
S2: carrying out hydrothermal reaction on zinc salt, a sulfur source and an organic carbon source serving as raw materials, collecting precipitates and drying after the reaction is finished to obtain a composite material precursor, and roasting the composite material precursor in an inert atmosphere to obtain the ZnS/C composite material;
s3 SnO prepared in the step S12The material is mixed with the ZnS/C composite material prepared in the step S2 in proportion to prepare the ZnS/C-SnO negative electrode material of the sodium-ion battery2。
To further illustrate the technical effects of the present invention, the following description will be given with reference to specific examples.
Example 1: preparation of ZnS/C-SnO by using tin mud2Composite material
Firstly, zinc acetate, sodium sulfide and anhydrous glucose are taken as raw materials, and 2.153g of C is weighed4H6O4Zn·2H2O, 4.712g of Na2S·9H2Dissolving O and 5.454g anhydrous glucose in 150mL distilled water to form clear transparent solution, transferring into a reaction kettle, performing hydrothermal reaction at 180 deg.C for 12h, and separatingPerforming heart-washing-ultrasonic dispersion, washing and precipitating with distilled water and anhydrous ethanol for three times, drying at 60 deg.C for 12 hr to obtain light gray precursor, and performing N precipitation2Calcining for 2h at 750 ℃ in atmosphere to obtain the ZnS/C material.
Secondly, in order to remove the influence of impurity ions, the sticky tin mud directly obtained from a production workshop is respectively cleaned by distilled water/absolute ethyl alcohol, then the solution is centrifugally separated and repeatedly cleaned for 3 times, and the sticky tin mud is placed in a drying box for drying at 60 ℃ for 10 hours to obtain light yellow green powder SnO2。
Thirdly, adopting a mechanical ball milling method for dry milling, namely ZnS/C and SnO2According to the mass ratio of 1:1, mixing, wherein the ball-material ratio is about 30:1, the rotating speed is 200 r/min, and the ball milling time is 10h to prepare the ZnS/C-SnO2 composite material.
Referring to FIG. 1, the product ZnS/C-SnO of this example2XRD spectrum of composite material, ZnS and SnO are shown in the figure2Characteristic diffraction peak of (2) indicating that the composite material contains ZnS and SnO2。
In FIG. 2, a, b, C, d are ZnS/C-SnO products of this example, respectively2SEM images of the composite material at different magnifications. As shown in the figure, the surface of the synthetic material is smooth, the particle size is small, and the particle size is uniform. There is also some agglomeration, which consists of smaller particles, which are referred to as secondary particles.
FIG. 3 a shows ZnS/C-SnO as a product of this example2The electronic image of the composite (marks 91, 92, 93), b, c, d of fig. 3 are EDS analysis spectra of the positions of the marks 91, 92, 93 on the electronic image corresponding to a, respectively. Fig. 4 is a table of energy spectrum element analysis corresponding to EDS analysis spectra 91, 92, 93 of fig. 3. It can be seen from fig. 4 that the weight percentages of the elements Zn and Sn are substantially close to 1:1, which is completely consistent with the initial charge ratio.
Example 2: preparation of ZnS/C-SnO by using tin mud2Composite material
Firstly, zinc acetate, sodium sulfide and anhydrous glucose are taken as raw materials, and 2.153g of C is weighed4H6O4Zn·2H2O, 4.712g of Na2S·9H2O and 5.454g of Anhydrous glucoseDissolving in 150mL of distilled water to form a clear transparent solution, transferring into a reaction kettle, performing hydrothermal reaction at 180 ℃ for 12h, centrifuging, washing, performing ultrasonic dispersion, washing and precipitating with distilled water and absolute ethyl alcohol for three times, drying at 60 ℃ for 12h to obtain a light gray precursor, and performing N-phase precipitation with a solvent2Calcining for 2h at 750 ℃ in atmosphere to obtain the ZnS/C material.
Secondly, in order to remove the influence of impurity ions, the sticky tin mud directly obtained from a production workshop is respectively cleaned by distilled water/absolute ethyl alcohol, then the solution is centrifugally separated and repeatedly cleaned for 3 times, and the sticky tin mud is placed in a drying box for drying at 60 ℃ for 10 hours to obtain light yellow green powder SnO2。
Thirdly, adopting a mechanical ball milling method for dry milling, namely ZnS/C and SnO2According to the mass ratio of 1:1 mixing, ball to feed ratio of about 30:1, rotating
The speed is 200 r/min, the ball milling time is 1h to prepare ZnS/C-SnO2A composite material.
ZnS/C-SnO prepared in this example2The composite material is used as an active material of a negative electrode of a sodium ion battery, and is mixed with acetylene black and a binder PVDF/NMP according to a mass ratio of 70: 20: 10 to prepare slurry, and then coating the slurry on a copper foil to form a film. Vacuum drying at 80 deg.C for 12 hr, cutting into pieces and tabletting, wherein the weight of active substance in the electrode slice is about 1 mg. A pure sodium sheet is taken as a counter electrode, sodium perchlorate electrolyte (NC-008) and Whatman glass microfiber membrane with the model of GF/D are used, and the CR2025 type button half cell is assembled in a glove box filled with argon. In the experiment, a battery performance tester LAND2001CT is used for carrying out charging and discharging and cycle performance tests, and the voltage range is 0.01-2.5V. The rate capability and coulombic efficiency curves of the cell were tested and the results are shown in figure 5. From this it can be seen that ZnS/C-SnO2The charging and discharging specific capacity of the composite material shows a stepwise gradual decrease along with the change of the current density, and when the current density is reduced to 0.05 A.g again-1In the process, the charging and discharging specific capacity is obviously increased, which shows that the material obtained in the embodiment has good capacity recovery. It is also clear from FIG. 5 that ZnS/C-SnO at various current densities2The composite material shows good specific capacity. It is first 0.05 A.g-1Specific discharge capacity at current density977.2mAh g-1The charging specific capacity is 556.4mAh g-1. When the current density is reduced again and returns to 0.05A-g-1The specific discharge capacity still remains 418.7mAh g-1The charging specific capacity is 405.2 mAh.g-1After the circulation is continued for 30 times, the charging and discharging specific capacity is still maintained at 324.1mAh g-1/330.1mAh·g-1. As can be seen, the ZnS/C-SnO obtained in this example2The composite material shows very good capacity recovery and capacity retention, which is also one of the most important performance indexes for measuring electrode materials.
Example 3: preparation of ZnS/C-SnO by using tin mud2Composite material
Firstly, zinc acetate, sodium sulfide and anhydrous glucose are taken as raw materials, and 2.153g of C is weighed4H6O4Zn·2H2O, 4.712g of Na2S·9H2Dissolving O and 5.454g anhydrous glucose in 150mL distilled water to form clear transparent solution, transferring into a reaction kettle, performing hydrothermal reaction at 180 deg.C for 12h, centrifuging, washing, ultrasonically dispersing, washing with distilled water and anhydrous ethanol for three times, precipitating, drying at 60 deg.C for 12h to obtain light gray precursor, and adding N2Calcining for 2h at 750 ℃ in atmosphere to obtain the ZnS/C material.
Secondly, in order to remove the influence of impurity ions, the sticky tin mud directly obtained from a production workshop is respectively cleaned by distilled water/absolute ethyl alcohol, then the solution is centrifugally separated and repeatedly cleaned for 3 times, and the sticky tin mud is placed in a drying box for drying at 60 ℃ for 10 hours to obtain light yellow green powder SnO2。
Thirdly, adopting a mechanical ball milling method for dry milling, namely ZnS/C and SnO2According to the mass ratio of 1:1 mixing, the ball-material ratio is about 30:1, the rotating speed is 200 r/min, and the ball milling time is 5h to prepare ZnS/C-SnO2A composite material.
ZnS/C-SnO prepared in this example2The composite material is used as an active material of a negative electrode of a sodium ion battery, and is mixed with acetylene black and a binder PVDF/NMP according to a mass ratio of 70: 20: 10 to prepare slurry, and then coating the slurry on a copper foil to form a film. Vacuum drying at 80 deg.C for 12 hr, cutting into pieces and tabletting, wherein the weight of active substance in the electrode slice is about 1 mg. Taking pure sodium tablets as pairsElectrode, sodium perchlorate as electrolyte (NC-008) with a formula of 1.0 mol.L-1NaClO4(EC: EDC 1:1 Vol% with 5% FEC), Whatman glass microfiber membrane, model GF/D, assembled into CR2025 button half-cell in argon filled glove box. In the experiment, a battery performance tester LAND2001CT is used for carrying out charging and discharging and cycle performance tests, and the voltage range is 0.01-2.5V. The cell was tested for charge and discharge performance and the results are shown in FIG. 6 as ZnS/C-SnO2The composite material is at 100 mA.g-1Under the current density, the curves distributed on the upper right side in the graph correspond to charging curves 1st, 2nd, 3rd, 4th and 5th from bottom to top in sequence according to the constant current charging and discharging curves of the first 5 times, and the curves distributed on the lower right side in the graph correspond to discharging curves 1st, 2nd, 3rd, 4th and 5th from top to bottom in sequence. The thick black line in the drawing is a discharge curve from 2 to 5 times of discharge, and since the electrode material has little discharge specific capacity decay, 4 curves are almost overlapped (the thick black line in the drawing). Visible, ZnS/C-SnO2The first charge-discharge specific capacity of the composite material is 494.9 mAh.g-1/909.0mAh·g-1The first coulombic efficiencies are 54.4% respectively, and the lithium ion battery has good charge-discharge specific capacity.
Example 4: preparation of ZnS/C-SnO by using tin mud2Composite material
Firstly, zinc acetate, sodium sulfide and anhydrous glucose are taken as raw materials, and 2.153g of C is weighed4H6O4Zn·2H2O, 4.712g of Na2S·9H2Dissolving O and 5.454g anhydrous glucose in 150mL distilled water to form clear transparent solution, transferring into a reaction kettle, performing hydrothermal reaction at 180 deg.C for 12h, centrifuging, washing, ultrasonically dispersing, washing with distilled water and anhydrous ethanol for three times, precipitating, drying at 60 deg.C for 12h to obtain light gray precursor, and adding N2Calcining for 2h at 750 ℃ in atmosphere to obtain the ZnS/C material.
Secondly, in order to remove the influence of impurity ions, the sticky tin mud directly obtained from a production workshop is respectively cleaned by distilled water/absolute ethyl alcohol, then the solution is centrifugally separated and repeatedly cleaned for 3 times, and the sticky tin mud is placed in a drying box for drying at 60 ℃ for 10 hours to obtain light yellow green powder SnO2。
Thirdly, mechanical balls are adoptedDry milling by ZnS/C and SnO2According to the mass ratio of 1:1 mixing, the ball-material ratio is about 30:1, the rotating speed is 200 r/min, and the ball milling time is 15h to prepare ZnS/C-SnO2A composite material.
ZnS/C-SnO prepared in this example2The composite material is used as an active material of a negative electrode of a sodium ion battery, and is mixed with acetylene black and a binder PVDF/NMP according to a mass ratio of 70: 20: 10 to prepare slurry, and then coating the slurry on a copper foil to form a film. Vacuum drying at 80 deg.C for 12 hr, cutting into pieces and tabletting, wherein the weight of active substance in the electrode slice is about 1 mg. Pure sodium sheet is taken as a counter electrode, sodium perchlorate is taken as electrolyte (NC-008), and the formula is 1.0 mol.L-1NaClO4(EC: EDC 1:1 Vol% with 5% FEC), Whatman glass microfiber membrane, model GF/D, assembled into CR2025 button half-cell in argon filled glove box. In the experiment, a battery performance tester LAND2001CT is used for carrying out charging and discharging and cycle performance tests, and the voltage range is 0.01-2.5V. The cycling performance and coulombic efficiency curves of the cells were tested and the results are shown in figure 7. From this it can be seen that ZnS/C-SnO2Composite material 100mA g-1And200 mA · g-1The charging and discharging specific capacity of the constant-current circulation curve is gradually reduced along with the increase of the circulation times in the first 50 times of circulation, and the charging and discharging specific capacity of the material is slowly reduced along with the reduction of the circulation times in the last 50 times of circulation. At 100mA · g-1And200 mA · g-1Under the current density, the discharge capacity after 100 cycles is 59.6mAh g-1217.1mAh g-1The discharge capacity decay rates per cycle were 0.714% and 0.735%, respectively, and it can also be seen from fig. 7 that the coulombic efficiency remained between 97% and 99% after the 5th cycle. Thus, the ZnS/C-SnO prepared in this example2The composite material has very reasonable cycling stability.
Example 5: preparation of ZnS/C-SnO by using tin mud2Composite material
Firstly, zinc acetate, sodium sulfide and anhydrous glucose are taken as raw materials, and 2.153g of C is weighed4H6O4Zn·2H2O, 4.712g of Na2S·9H2O and 5.454g of anhydrous glucose were simultaneously dissolved in 150mL of distilled water to form a clear solutionTransferring the transparent solution into a reaction kettle, performing hydrothermal reaction at 180 ℃ for 12h, centrifuging, washing, performing ultrasonic dispersion, washing and precipitating with distilled water and absolute ethyl alcohol for three times, drying at 60 ℃ for 12h to obtain light gray precursor, and performing N-phase precipitation2Calcining for 2h at 750 ℃ in atmosphere to obtain the ZnS/C material.
Secondly, in order to remove the influence of impurity ions, the sticky tin mud directly obtained from a production workshop is respectively cleaned by distilled water/absolute ethyl alcohol, then the solution is centrifugally separated and repeatedly cleaned for 3 times, and the sticky tin mud is placed in a drying box for drying at 60 ℃ for 10 hours to obtain light yellow green powder SnO2。
Thirdly, adopting a mechanical ball milling method for dry milling, namely ZnS/C and SnO2According to the mass ratio of 2: 1 mixing, the ball-material ratio is about 30:1, the rotating speed is 200 r/min, and the ball milling time is 5h to prepare ZnS/C-SnO2A composite material.
Example 6: preparation of ZnS/C-SnO by using tin mud2Composite material
Firstly, zinc acetate, sodium sulfide and anhydrous glucose are taken as raw materials, and 2.153g of C is weighed4H6O4Zn·2H2O, 4.712g of Na2S·9H2Dissolving O and 5.454g anhydrous glucose in 150mL distilled water to form clear transparent solution, transferring into a reaction kettle, performing hydrothermal reaction at 180 deg.C for 12h, centrifuging, washing, ultrasonically dispersing, washing with distilled water and anhydrous ethanol for three times, precipitating, drying at 60 deg.C for 12h to obtain light gray precursor, and adding N2Calcining for 2h at 750 ℃ in atmosphere to obtain the ZnS/C material.
Secondly, in order to remove the influence of impurity ions, the sticky tin mud directly obtained from a production workshop is respectively cleaned by distilled water/absolute ethyl alcohol, then the solution is centrifugally separated and repeatedly cleaned for 3 times, and the sticky tin mud is placed in a drying box for drying at 60 ℃ for 10 hours to obtain light yellow green powder SnO2。
Thirdly, adopting a mechanical ball milling method for dry milling, namely ZnS/C and SnO2According to the mass ratio of 2: 1 mixing, the ball-material ratio is about 30:1, the rotating speed is 200 r/min, and the ball milling time is 10h to prepare ZnS/C-SnO2A composite material.
Example 7: preparation of ZnS/C-SnO by using tin mud2Composite materialMaterial
Using zinc acetate, sodium sulfide and anhydrous glucose as raw materials, weighing 2.153g of C4H6O4Zn·2H2O, 4.712g of Na2S·9H2Dissolving O and 5.454g anhydrous glucose in 150mL distilled water to form clear transparent solution, transferring into a reaction kettle, performing hydrothermal reaction at 180 deg.C for 12h, centrifuging, washing, ultrasonically dispersing, washing with distilled water and anhydrous ethanol for three times, precipitating, drying at 60 deg.C for 12h to obtain light gray precursor, and adding N2Calcining for 2h at 750 ℃ in atmosphere to obtain the ZnS/C material.
In order to remove the influence of impurity ions, the sticky tin mud directly obtained from a production workshop is respectively cleaned by distilled water/absolute ethyl alcohol, then the solution is centrifugally separated, repeatedly cleaned for 3 times, and dried in a drying oven at 60 ℃ for 10 hours to obtain light yellow green powder SnO2。
And (2) dry grinding by adopting a mechanical ball grinding method, wherein the weight ratio of ZnS/C to SnO2 is 3: 1 mixing, the ball-material ratio is about 30:1, the rotating speed is 200 r/min, and the ball milling time is 10h to prepare ZnS/C-SnO2A composite material.
Example 8: preparation of ZnS/C-SnO by using tin mud2Composite material
Using zinc acetate, sodium sulfide and anhydrous glucose as raw materials, weighing 2.153g of C4H6O4Zn·2H2O, 4.712g of Na2S·9H2Dissolving O and 5.454g anhydrous glucose in 150mL distilled water to form clear transparent solution, transferring into a reaction kettle, performing hydrothermal reaction at 180 deg.C for 12h, centrifuging, washing, ultrasonically dispersing, washing with distilled water and anhydrous ethanol for three times, precipitating, drying at 60 deg.C for 12h to obtain light gray precursor, and adding N2Calcining for 2h at 750 ℃ in atmosphere to obtain the ZnS/C material.
In order to remove the influence of impurity ions, the sticky tin mud directly obtained from a production workshop is respectively cleaned by distilled water/absolute ethyl alcohol, then the solution is centrifugally separated, repeatedly cleaned for 3 times, and dried in a drying oven at 60 ℃ for 10 hours to obtain light yellow green powder SnO2。
Adopting a mechanical ball milling method for dry milling, ZnSC and SnO2According to the mass ratio of 4: 1 mixing, the ball-material ratio is about 30:1, the rotating speed is 200 r/min, and the ball milling time is 10h to prepare ZnS/C-SnO2A composite material.
The above examples and test results prove that the negative electrode material ZnS/CSnO of the sodium-ion battery prepared by the method of the invention2The performance requirements on the negative electrode material of the sodium ion battery can be met, the specific capacity is good, the initial capacity is high, the ideal cycle stability is achieved, and the position of the sodium ion battery in an energy storage system is promoted.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.

Claims (10)

1. Preparation of sodium ion battery negative electrode material ZnS/C-SnO by using tin mud2Characterized in that it comprises:
s1: washing the tin mud by using distilled water and washing and drying the tin mud by using absolute ethyl alcohol to obtain SnO2A material;
s2: carrying out hydrothermal reaction on zinc salt, a sulfur source and an organic carbon source serving as raw materials, collecting precipitates and drying after the reaction is finished to obtain a composite material precursor, and roasting the composite material precursor in an inert atmosphere to obtain the ZnS/C composite material;
s3 SnO prepared in the step S12The material is mixed with the ZnS/C composite material prepared in the step S2 in proportion to prepare the ZnS/C-SnO negative electrode material of the sodium-ion battery2。
2. The method according to claim 1, wherein in the step S1, the mixing volume ratio of the tin mud and the distilled water or the absolute ethyl alcohol is 1-5: 6.
3. The method according to claim 2, wherein in step S1, the washing comprises more than 3 times, that is, more than 3 times of distilled water washing and more than 3 times of absolute ethanol washing, and the distilled water washing and the absolute ethanol washing are sequentially performed or alternately performed.
4. The method of claim 3, wherein in step S1, the drying in step S1 is performed at 60-80 ℃ for 10-12h to obtain light yellow-green powder (SnO)2A material.
5. The method according to claim 1, wherein in step S2, the zinc salt is one or more of zinc acetate, zinc nitrate and zinc chloride; the sulfur source is one or more of sulfur powder, sodium sulfide and thiourea; the organic carbon source is one or more of glucose, sucrose, starch and citric acid; and the zinc salt, the sulfur source and the organic carbon source are dissolved in water and then transferred to a hydrothermal reaction kettle for sealing reaction.
6. The method according to claim 5, wherein in step S2, the hydrothermal reaction temperature is 120-180 ℃ and the reaction time is 10-14 h.
7. The method according to claim 6, wherein in step S2, after the hydrothermal reaction is finished, the precipitate is collected, and then the hydrothermal reaction product is subjected to centrifugation-washing-ultrasonic dispersion-drying treatment, so as to obtain a composite material precursor; and (3) performing centrifugal separation to obtain a precipitate of the hydrothermal reaction, washing by respectively washing with distilled water and absolute ethyl alcohol for more than 3 times, performing ultrasonic dispersion by loading ultrasonic waves in the washing process, and drying at 60-80 ℃ for 10-12 h.
8. The method according to claim 7, wherein in step S2, the composite material precursor is placed in a nitrogen or argon atmosphere and baked at 600-900 ℃ for 2-5 h to obtain the ZnS/C composite material.
9. Root of herbaceous plantThe method according to claim 1, wherein in step S3: SnO prepared from S1 by adopting dry ball milling mode2The material is mixed with a ZnS/C composite material prepared from S2 according to a mass ratio of 1: 1-4, ball milling is carried out for 1-15 h at a ball-to-material ratio of 20-30: 1 and 200-800 r/min, and a negative electrode material ZnS/C-SnO of the sodium ion battery is prepared2。
10. A sodium ion battery negative electrode material prepared by the method of any one of claims 1 to 9.
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