CN109378458A - It is a kind of to utilize the clay standby anode material of lithium-ion battery ZnS/C-SnO of tin2Method - Google Patents

It is a kind of to utilize the clay standby anode material of lithium-ion battery ZnS/C-SnO of tin2Method Download PDF

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CN109378458A
CN109378458A CN201811228765.5A CN201811228765A CN109378458A CN 109378458 A CN109378458 A CN 109378458A CN 201811228765 A CN201811228765 A CN 201811228765A CN 109378458 A CN109378458 A CN 109378458A
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sno
zns
composite material
tin
ion battery
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CN109378458B (en
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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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Northeastern University China
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The clay standby anode material of lithium-ion battery ZnS/C-SnO of tin is utilized the present invention relates to a kind of2Method comprising: S1: tin mud is washed, is dried, SnO is obtained2Material；S2: one step hydro thermal method prepares ZnS/C composite material: carrying out hydro-thermal reaction by raw material of zinc salt, sulphur source and organic carbon source, precipitating, drying are collected after reaction, composite material precursor is obtained, composite material precursor is placed in inert atmosphere and is roasted, obtains ZnS/C composite material；S3: SnO prepared by step S12Material mixes in proportion with ZnS/C composite material prepared by step S2, and anode material of lithium-ion battery ZnS/C-SnO is made2.The problem of present invention does not obtain appropriate recycling and reusing to the tin mud generated in tin plating technique solves SnO using the clay standby anode material of lithium-ion battery of tin2The problem of involving great expense effectively reduces the cost of raw material, is more in line with the theory of sodium-ion battery low cost, realizes the comprehensive utilization of resource.

Description

It is a kind of to utilize the clay standby anode material of lithium-ion battery ZnS/C-SnO of tin2Method
Technical field
The present invention relates to battery material technical fields, and in particular to a kind of to utilize the clay standby anode material of lithium-ion battery of tin ZnS/C-SnO2Method.
Background technique
Important technology of the secondary cell as energy stores and conversion, in new energy field in occupation of very importantly Position.To cope with energy crisis, the secondary cell of the efficient convenient and suitable extensive energy storage of exploitation is had a very important significance.By It is rare in lithium resource, lithium salts price continuous rise is caused, is remained high, this seriously will restrict lithium ion battery in energy storage field Sustainable development.In contrast, sodium element has similar chemical property with elemental lithium, and sodium element content is extremely abundant, this So that the cost of sodium-ion battery is well below lithium ion battery.Therefore, sodium-ion battery is expected to replace lithium in energy-storage system Ion battery.
Anode material of lithium-ion battery is responsible for providing low oxidation-reduction potential, has to its safety and validity very high Requirement.At present in the correlative study of anode material of lithium-ion battery, main negative electrode material has metal oxide and carbon material, But most metal oxide costs is very high, misfits with the theory of sodium-ion battery low cost, and negative electrode material is initial Capacity is not high, and cycle performance is not ideal enough always.The oxide of tin is obtained because of specific capacity with higher and good electric conductivity Extensive concern there is ideal cyclical stability as the negative electrode material of sodium-ion battery.Tin oxide and sodium ion can Conversion reaction, SnO occurs2Theoretical capacity with higher.Mainly there are two processes for embedding sodium for the first time by Sn: being initially formed NaxSn(x ~0.5) alloy, and then react and form Na15Sn4(x=3.75), reach 420% volume expansion, but huge volume expansion It does not cause the collapsing of material and is crushed, the structure of material remains intact substantially.This important discovery illustrate Sn as sodium from Sub- cell negative electrode material theoretically can be realized good cyclical stability, but SnO2The price is very expensive limits its business Change process.
It, all can be because of Sn in the electroplate liquid of conventional tin plating technique2+In anode region, betatopic is oxidized to Sn4+And generate tin mud. The generation of tin mud leads to Sn in plating solution2+Loss, increase the consumption of tin anode, thus cause production cost higher.Tin mud Generation means economic loss, and the discharge of tin mud will aggravate the pollution to environment.The prior art to the processing of tin mud very It is undesirable, do not obtain appropriate recycling and reusing.Meanwhile the technological process of production of tin oxide extremely complex leads to commodity SnO2 The price is very expensive.
In summary problem, the object of the present invention is to provide one kind properly to recycle to tin mud, and with low cost system The method of standby anode material of lithium-ion battery.
Summary of the invention
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provides a kind of utilization clay standby sodium-ion battery cathode material of tin Expect ZnS/C-SnO2Method, first pass through tin mud obtain SnO2, then it is used for preparing anode material of lithium-ion battery ZnS/C- SnO2, on the one hand the Sn in tin mud is recycled, is reduced environmental pollution, on the other hand realizes and is prepared with lower cost Cell negative electrode material of good performance realizes the comprehensive utilization of resource.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
It is a kind of to utilize the clay standby anode material of lithium-ion battery ZnS/C-SnO of tin2Method comprising:
S1: tin mud is washed, is dried, SnO is obtained2Material；
S2: one step hydro thermal method prepares ZnS/C composite material: it is anti-to carry out hydro-thermal using zinc salt, sulphur source and organic carbon source as raw material It answers, collects precipitating, drying after reaction, obtain composite material precursor, composite material precursor is placed in inert atmosphere Roasting, obtains ZnS/C composite material；
S3: SnO prepared by step S12Material mixes in proportion with ZnS/C composite material prepared by step S2, and sodium is made Ion battery cathode material ZnS/C-SnO2。
Wherein, step S1 and S2 does not have sequencing, and sequence is interchangeable in other words.
Preferably, in step S1, carrying out washing to tin mud includes: that distillation water washing and dehydrated alcohol wash；And when washing, The mixed volume ratio of tin mud and distilled water or dehydrated alcohol is about 1~5:6.
Distill the SO in the removable tin mud of water washing3The water soluble acid or salt less with other contents；And dehydrated alcohol is washed It washs and almost can remove mixed whole organic matters in tin mud.
Preferably, in step S1, the washing includes 3 times or more, that is, includes 3 times or more distillation water washings and 3 times or more Dehydrated alcohol washing distills water washing and carries out or intersect for either order without water washing to carry out.
Preferably, the drying in step S1 is dry at 60~80 DEG C, and 10~12h of drying time obtains pistac Powder, i.e. SnO2Material.
After above-mentioned washing and drying, SnO obtained2SnO in material2Purity reach 95% or more, also containing micro Silica and the insoluble metal oxide such as iron oxide, aluminium oxide, bismuth oxide.This kind of oxide impurity also need not deliberately be gone It removes, the moderate doping that just can be used as to anode material of lithium-ion battery of content, and can also be further by chanza Improve the circulating battery stability of battery material.In other words, just because of the SnO contained high in tin mud2With micro- oxide contained Impurity, which all has, is suitable for production anode material of lithium-ion battery, thus the method according to the invention handles tin mud, not only makes tin mud Recovery process become more simply also to be able to achieve the comprehensive utilization of high value.
Preferably, in step S2, the zinc salt is one or more of zinc acetate, zinc nitrate, zinc chloride；The sulphur source For one or more of sulphur powder, vulcanized sodium, thiocarbamide；The organic carbon source is glucose, sucrose, starch, one in citric acid Kind is several；The zinc salt, sulphur source, organic carbon source are soluble in water, are then transferred to hydrothermal reaction kettle sealing reaction.
Preferably, in step S2, the temperature of the hydro-thermal reaction is 120~180 DEG C, 10~14h of reaction time.
Preferably, in step S2, precipitating is collected after hydro-thermal reaction, then be centrifuged by hydro-thermal reaction product- Washing-ultrasonic disperse-drying and processing, obtains composite material precursor later.Wherein, it is centrifugally separating to obtain the precipitating of hydro-thermal reaction Object, washing are respectively washed 3 times or more using distilled water and dehydrated alcohol, and ultrasonic disperse is that load is ultrasonic in the process of washing Wave finally dries sediment after washing with increasing washing effect (removal foreign ion) and improving the homogeneity of sediment Dry, drying is the dry 10-12h at 60-80 DEG C.
Wherein, in step S2, composite material precursor is placed in nitrogen or argon atmosphere, in 600~900 DEG C roast 2~ 5h obtains ZnS/C composite material.
Preferably, in step S3: the SnO for being prepared S1 using dry ball milling mode2Material and ZnS/C prepared by S2 are compound Material 1:1 in mass ratio~4 mixing, ratio of grinding media to material are 20~30:1, and sodium ion is made in 1~15h of ball milling under 200~800r/min Cell negative electrode material ZnS/C-SnO2。
(3) beneficial effect
The beneficial effects of the present invention are:
(1) aiming at the problem that tin mud generated in tin plating technique does not obtain appropriate recycling and reusing, the present invention uses tin Clay standby anode material of lithium-ion battery realizes that the synthesis high value of resource recycles.
Contain about 86.7% SnO in tin mud2, 9~9.4% sulfur trioxide, have used in tin plating technique on a small quantity Machine additive, remaining accounts for about 1% for water, iron oxide, silica, bismuth oxide, aluminium oxide etc., thus the main component of tin mud is exactly SnO2.The present invention is using tin mud as the raw material of anode material of lithium-ion battery, it is only necessary to remove sulfur trioxide therein and organic The impurity such as object additive (mainly phenolsulfonate and compound aromatic base), C, O, S constituent content are after carrying out washing treatment It reduces, and Sn elemental purity increases, after washed, the ingredient in former electroplate liquid contained in tin mud is dissolved in cleaning solution, Purity is high can be obtained of about 95% SnO2With the oxides such as micro iron oxide, silica, bismuth oxide and aluminium oxide, these oxygen Compound not only will not influence the chemical property of anode material of lithium-ion battery, moreover it is possible to which playing chanza further improves electricity The initial capacity and circulating battery stability of pond material.Therefore, one aspect of the present invention is realized with better simply technical process to tin On the other hand the recycling of mud prepares cell negative electrode material of good performance with lower cost.
(2) recycling of the present invention to tin mud need to only carry out carrying out washing treatment, can be used after dry.Operating process is very simple Single, the operation of recovery process, equipment cost are low, greatly reduce in tin plating technique because of economic damage caused by the generation of tin mud It loses.
It (3) is SnO with tin mud in the present invention2Source, solve SnO2The problem of involving great expense effectively reduces raw material Cost, be more in line with the theory of sodium-ion battery low cost, realize the comprehensive utilization of resource.
(4) anode material of lithium-ion battery ZnS/C-SnO made from the method for the present invention2With preferable specific capacity, SnO2Make Electrode material has good stability, meets the performance requirement to anode material of lithium-ion battery, i.e., with higher first Beginning capacity and ideal cyclical stability.
(5) present invention obtains ZnS/C composite material by one step hydro thermal method, and technical process is simple, operating condition temperature With.The present invention can prepare the ZnS/C-SnO haveing excellent performance by mechanical attrition method2Composite material, technical process is simple, can It commercially produces.
The present invention is low for the initial capacity of metal oxide negative electrode material using the by-product tin mud of tin plating technique as raw material It is poor with cyclical stability and the problems such as it involves great expense, it proposes a kind of preparation method of anode material of lithium-ion battery, is made Negative electrode material so that battery is had excellent charging and discharging capacity and ideal cyclical stability, solve SnO2It involves great expense Defect realizes the comprehensive utilization of resource simultaneously, and the tin mud more generated in tin plating technique, which provides a new recycling, to be thought Road.
Detailed description of the invention
Fig. 1 is the product ZnS/C-SnO of embodiment 12Composite material XRD spectra.
A, b, c, d of Fig. 2 is respectively the product ZnS/C-SnO of embodiment 32Composite material is under different amplification SEM figure.
The a of Fig. 3 is the product ZnS/C-SnO of embodiment 32The electronic image (label 91,92,93) of composite material, Fig. 3's B, c, d are respectively the EDS analysis of spectra of 91,92,93 position of label on the electronic image of corresponding a.
Fig. 4 is the power spectrum elemental analysis table of EDS analytical spectra Figure 91,92,93 of corresponding diagram 3.
Fig. 5 is ZnS/C-SnO in embodiment 22It is tested after the sodium-ion battery cathode assembled battery of composite material production Circulation performance and coulombic efficiency curve.
Fig. 6 is ZnS/C-SnO in embodiment 32Composite material 100mAg-1The sodium-ion battery cathode assembled battery of production Afterwards, the charging and discharging curve under constant current.
Fig. 7 is ZnS/C-SnO in embodiment 42It is tested after the sodium-ion battery cathode assembled battery of composite material production Cycle performance and coulombic efficiency curve.
Specific embodiment
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair It is bright to be described in detail.
Basic ideas of the invention are as follows: using the by-product tin mud of tin plating technique as raw material, handled with simple process The high-purity SnO containing doping oxide is made in tin mud2, and be used for the product to make anode material of lithium-ion battery, by this Negative electrode material enables sodium-ion battery to obtain excellent charging and discharging capacity and ideal stable circulation for making battery cathode Property.
A kind of utilization clay standby anode material of lithium-ion battery ZnS/C-SnO of tin provided by the invention2Method, packet It includes:
S1: tin mud is washed, is dried, SnO is obtained2Material；
Specifically, carrying out washing to tin mud includes: that distillation water washing and dehydrated alcohol wash；And when washing, tin mud and steaming Distilled water or the mixed volume ratio of dehydrated alcohol are about 1~5:6.Distill the SO in the removable tin mud of water washing3With other contents compared with Few water soluble acid or salt；And dehydrated alcohol washing almost can remove mixed whole organic matters in tin mud.
Washing includes 3 times or more, that is, includes the washing of 3 times or more distillation water washings and 3 times or more dehydrated alcohol, distillation washing It washs and carries out or intersect for either order without water washing to carry out.
Wherein, drying is dry at 60~80 DEG C, and 10~12h of drying time obtains pistac powder, i.e. SnO2Material Material.
After above-mentioned washing and drying, SnO obtained2SnO in material2Purity reach 95% or so, also containing micro Silica and the insoluble metal oxide such as iron oxide, aluminium oxide, bismuth oxide.This kind of oxide impurity also need not deliberately be gone It removes, because of its doping that can be used as anode material of lithium-ion battery, and battery can also further be improved by chanza The initial capacity and circulating battery stability of material.In other words, just because of the SnO contained high in tin mud2With micro- oxidation contained Object impurity, which all has, is suitable for production anode material of lithium-ion battery, thus the method according to the invention handles tin mud, not only makes tin The recovery process of mud becomes the comprehensive utilization for being more simply also able to achieve high value.
S2: one step hydro thermal method prepares ZnS/C composite material: it is anti-to carry out hydro-thermal using zinc salt, sulphur source and organic carbon source as raw material It answers, collects precipitating, drying after reaction, obtain composite material precursor, composite material precursor is placed in inert atmosphere Roasting, obtains ZnS/C composite material；
S3: SnO prepared by step S12Material mixes in proportion with ZnS/C composite material prepared by step S2, and sodium is made Ion battery cathode material ZnS/C-SnO2。
Technical effect in order to further illustrate the present invention, is illustrated below in conjunction with specific embodiment.
Embodiment 1: the clay standby ZnS/C-SnO of tin is utilized2Composite material
1. weighing the C of 2.153g using zinc acetate, vulcanized sodium and DEXTROSE ANHYDROUS as raw material4H6O4Zn·2H2O、4.712g Na2S·9H2O and 5.454g DEXTROSE ANHYDROUS is dissolved in 150mL distilled water simultaneously after formation clear transparent solutions, moves into reaction For kettle at 180 DEG C after hydro-thermal reaction 12h, centrifugation-washing-ultrasonic disperse washs precipitating three with distilled water and dehydrated alcohol respectively Secondary, 60 DEG C of dry 12h obtain light gray presoma, after in N2750 DEG C of calcining 2h, obtain ZnS/C material in atmosphere.
2. the thick tin mud that will be directly obtained from workshop uses distillation for the influence for removing foreign ion respectively Water/washes of absolute alcohol tin mud is later centrifugated solution, cleans 3 times, is placed in drying box after 60 DEG C of dry 10h repeatedly Obtain pistac powder SnO2。
3. using mechanical attrition method dry grinding mode, ZnS/C and SnO2The mixing of 1:1 in mass ratio, ratio of grinding media to material is about 30:1, is turned Speed is 200 revs/min, and Ball-milling Time is that 10h prepares ZnS/C-SnO2Composite material.
It is the product ZnS/C-SnO of the present embodiment referring to Fig. 12Composite material XRD spectra shows ZnS and SnO in figure2's Characteristic diffraction peak indicates to contain ZnS and SnO in composite material2。
A, b, c, d of Fig. 2 is respectively the product ZnS/C-SnO of the present embodiment2Composite material is under different amplification SEM figure.Synthetic surfaces as shown in the figure are relatively smooth, and particle size is smaller, epigranular.There is showing for some reunions simultaneously As these aggregates are made of more little particle, these little particles are referred to as offspring.
The a of Fig. 3 is the product ZnS/C-SnO of the present embodiment2The electronic image (label 91,92,93) of composite material, Fig. 3 B, c, d be respectively 91,92,93 position of label on the electronic image of corresponding a EDS analysis of spectra.Fig. 4 is the EDS of corresponding diagram 3 The power spectrum elemental analysis table of analytical spectra Figure 91,92,93.As can be seen from Figure 4 the weight percent of element Zn and Sn connects substantially Nearly 1:1, this result fit like a glove with initial charge ratio.
Embodiment 2: the clay standby ZnS/C-SnO of tin is utilized2Composite material
1. weighing the C of 2.153g using zinc acetate, vulcanized sodium and DEXTROSE ANHYDROUS as raw material4H6O4Zn·2H2O、4.712g Na2S·9H2O and 5.454g DEXTROSE ANHYDROUS is dissolved in 150mL distilled water simultaneously after formation clear transparent solutions, moves into reaction For kettle at 180 DEG C after hydro-thermal reaction 12h, centrifugation-washing-ultrasonic disperse washs precipitating three with distilled water and dehydrated alcohol respectively Secondary, 60 DEG C of dry 12h obtain light gray presoma, after in N2750 DEG C of calcining 2h, obtain ZnS/C material in atmosphere.
2. the thick tin mud that will be directly obtained from workshop uses distillation for the influence for removing foreign ion respectively Water/washes of absolute alcohol tin mud is later centrifugated solution, cleans 3 times, is placed in drying box after 60 DEG C of dry 10h repeatedly Obtain pistac powder SnO2。
3. using mechanical attrition method dry grinding mode, ZnS/C and SnO2The mixing of 1:1 in mass ratio, ratio of grinding media to material is about 30:1, is turned Speed is 200 revs/min, and Ball-milling Time is that 1h prepares ZnS/C-SnO2Composite material.
By ZnS/C-SnO made from the present embodiment2Active material of the composite material as sodium-ion battery cathode, with acetylene Black, the binder PVDF/NMP ratio of 70:20:10 in mass ratio is mixed and made into slurry, is then coated on copper foil and forms a film.In 80 Cut-parts and tabletting after DEG C vacuum drying 12h, active material weight is in 1mg or so in electrode slice.It is to use electrode with pure sodium piece Sodium perchlorate electrolyte (NC-008), Whatman glass microfiber film, model GF/D are assembled in being full of argon gas glove box At CR2025 type button half-cell.Charge and discharge are carried out using LAND2001CT battery performance test instrument in experiment and cycle performance is surveyed Examination, voltage range are 0.01~2.5V.The high rate performance and coulombic efficiency curve of the battery are tested, it is as a result shown in Figure 5.By This can be seen that, ZnS/C-SnO2Composite material is gradually passed as the change charging and discharging capacity of current density shows staged Subtract, when current density is again decreased to 0.05Ag-1When, charging and discharging capacity significantly increases, and illustrates the present embodiment resulting materials With good capacity restorability.It can also be clearly seen from Fig. 5, under various different current densities, ZnS/C-SnO2It is multiple Condensation material shows good specific capacity.Its 0.05Ag for the first time-1Specific discharge capacity under current density is 977.2mAhg-1, charge specific capacity 556.4mAhg-1.When current density reduces again back to 0.05Ag-1When, specific discharge capacity still has 418.7mAh·g-1, charge specific capacity 405.2mAhg-1, charging and discharging capacity remains at after hereafter continuing cycling through 30 times 324.1mAh·g-1/330.1mAh·g-1.It can be seen that the resulting ZnS/C-SnO of the present embodiment2Composite material exhibits go out very Good capacity restorability and capacity retention is also to measure one of most important performance indicator of electrode material.
Embodiment 3: the clay standby ZnS/C-SnO of tin is utilized2Composite material
1. weighing the C of 2.153g using zinc acetate, vulcanized sodium and DEXTROSE ANHYDROUS as raw material4H6O4Zn·2H2O、4.712g Na2S·9H2O and 5.454g DEXTROSE ANHYDROUS is dissolved in 150mL distilled water simultaneously after formation clear transparent solutions, moves into reaction For kettle at 180 DEG C after hydro-thermal reaction 12h, centrifugation-washing-ultrasonic disperse washs precipitating three with distilled water and dehydrated alcohol respectively Secondary, 60 DEG C of dry 12h obtain light gray presoma, after in N2750 DEG C of calcining 2h, obtain ZnS/C material in atmosphere.
2. the thick tin mud that will be directly obtained from workshop uses distillation for the influence for removing foreign ion respectively Water/washes of absolute alcohol tin mud is later centrifugated solution, cleans 3 times, is placed in drying box after 60 DEG C of dry 10h repeatedly Obtain pistac powder SnO2。
3. using mechanical attrition method dry grinding mode, ZnS/C and SnO2The mixing of 1:1 in mass ratio, ratio of grinding media to material is about 30:1, is turned Speed is 200 revs/min, and Ball-milling Time is that 5h prepares ZnS/C-SnO2Composite material.
By ZnS/C-SnO made from the present embodiment2Active material of the composite material as sodium-ion battery cathode, with acetylene Black, the binder PVDF/NMP ratio of 70:20:10 in mass ratio is mixed and made into slurry, is then coated on copper foil and forms a film.In 80 Cut-parts and tabletting after DEG C vacuum drying 12h, active material weight is in 1mg or so in electrode slice.It is to electrode, high chlorine with pure sodium piece Sour sodium is electrolyte (NC-008), is formulated as 1.0molL-1NaClO4(EC:EDC is that 1:1Vol% adds 5%FEC), Whatman glass microfiber film, model GF/D are assembled into CR2025 type button half-cell in being full of argon gas glove box.It is real Test it is middle using LAND2001CT battery performance test instrument carry out charge and discharge and cycle performance test, voltage range be 0.01~ 2.5V.The charge-discharge performance of the battery is tested, as a result shown in Figure 6 is ZnS/C-SnO2Composite material is in 100mAg-1Electricity Under current density, first 5 times constant current charge-discharge curves, the curve of upper right side distribution is corresponding in turn to charging curve from bottom to up in figure 1st, 2nd, 3rd, 4th, 5th, in figure the curve of lower right side distribution be corresponding in turn to from top to bottom discharge curve 1st, 2nd, 3rd, 4th,5th.Heavy black in drawing is 2-5 discharge curve of electric discharge, seldom due to electrode material specific discharge capacity decaying, institute (heavy black in figure) is almost overlaped with 4 curves.As it can be seen that ZnS/C-SnO2Composite material first charge-discharge specific capacity 494.9mAh·g-1/909.0mAh·g-1, coulombic efficiency is respectively 54.4% for the first time, has good charging and discharging capacity.
Embodiment 4: the clay standby ZnS/C-SnO of tin is utilized2Composite material
1. weighing the C of 2.153g using zinc acetate, vulcanized sodium and DEXTROSE ANHYDROUS as raw material4H6O4Zn·2H2O、4.712g Na2S·9H2O and 5.454g DEXTROSE ANHYDROUS is dissolved in 150mL distilled water simultaneously after formation clear transparent solutions, moves into reaction For kettle at 180 DEG C after hydro-thermal reaction 12h, centrifugation-washing-ultrasonic disperse washs precipitating three with distilled water and dehydrated alcohol respectively Secondary, 60 DEG C of dry 12h obtain light gray presoma, after in N2750 DEG C of calcining 2h, obtain ZnS/C material in atmosphere.
2. the thick tin mud that will be directly obtained from workshop uses distillation for the influence for removing foreign ion respectively Water/washes of absolute alcohol tin mud is later centrifugated solution, cleans 3 times, is placed in drying box after 60 DEG C of dry 10h repeatedly Obtain pistac powder SnO2。
3. using mechanical attrition method dry grinding mode, ZnS/C and SnO2The mixing of 1:1 in mass ratio, ratio of grinding media to material is about 30:1, is turned Speed is 200 revs/min, and Ball-milling Time is that 15h prepares ZnS/C-SnO2Composite material.
By ZnS/C-SnO made from the present embodiment2Active material of the composite material as sodium-ion battery cathode, with acetylene Black, the binder PVDF/NMP ratio of 70:20:10 in mass ratio is mixed and made into slurry, is then coated on copper foil and forms a film.In 80 Cut-parts and tabletting after DEG C vacuum drying 12h, active material weight is in 1mg or so in electrode slice.It is to electrode, high chlorine with pure sodium piece Sour sodium is electrolyte (NC-008), is formulated as 1.0molL-1NaClO4(EC:EDC is that 1:1Vol% adds 5%FEC), Whatman glass microfiber film, model GF/D are assembled into CR2025 type button half-cell in being full of argon gas glove box.It is real Test it is middle using LAND2001CT battery performance test instrument carry out charge and discharge and cycle performance test, voltage range be 0.01~ 2.5V.The cycle performance and coulombic efficiency curve of the battery are tested, it is as a result shown in Figure 7.It will thus be seen that ZnS/C-SnO2 Composite material 100mAg-1And 200mAg-1Constant current cycle curve charging and discharging capacity in preceding 50 circulations is secondary with circulation Several increases are gradually successively decreased, and the charging and discharging capacity of material is decayed very slow with cycle-index in rear 50 circulations.? 100mA·g-1And 200mAg-1Under current density, discharge capacity is respectively 259.6mAhg after 100 circulations-1With 217.1mAh·g-1, each cyclic discharge capacity attenuation rate is respectively 0.714% and 0.735%, from Fig. 7 it can also be seen that from Coulombic efficiency is always held between 97%-99% after the 5th circulation.It follows that ZnS/C-SnO made from the present embodiment2 Composite material has the cyclical stability of very rationality.
Embodiment 5: the clay standby ZnS/C-SnO of tin is utilized2Composite material
1. weighing the C of 2.153g using zinc acetate, vulcanized sodium and DEXTROSE ANHYDROUS as raw material4H6O4Zn·2H2O、4.712g Na2S·9H2O and 5.454g DEXTROSE ANHYDROUS is dissolved in 150mL distilled water simultaneously after formation clear transparent solutions, moves into reaction For kettle at 180 DEG C after hydro-thermal reaction 12h, centrifugation-washing-ultrasonic disperse washs precipitating three with distilled water and dehydrated alcohol respectively Secondary, 60 DEG C of dry 12h obtain light gray presoma, after in N2750 DEG C of calcining 2h, obtain ZnS/C material in atmosphere.
2. the thick tin mud that will be directly obtained from workshop uses distillation for the influence for removing foreign ion respectively Water/washes of absolute alcohol tin mud is later centrifugated solution, cleans 3 times, is placed in drying box after 60 DEG C of dry 10h repeatedly Obtain pistac powder SnO2。
3. using mechanical attrition method dry grinding mode, ZnS/C and SnO2The mixing of 2:1 in mass ratio, ratio of grinding media to material is about 30:1, is turned Speed is 200 revs/min, and Ball-milling Time is that 5h prepares ZnS/C-SnO2Composite material.
Embodiment 6: the clay standby ZnS/C-SnO of tin is utilized2Composite material
1. weighing the C of 2.153g using zinc acetate, vulcanized sodium and DEXTROSE ANHYDROUS as raw material4H6O4Zn·2H2O、4.712g Na2S·9H2O and 5.454g DEXTROSE ANHYDROUS is dissolved in 150mL distilled water simultaneously after formation clear transparent solutions, moves into reaction For kettle at 180 DEG C after hydro-thermal reaction 12h, centrifugation-washing-ultrasonic disperse washs precipitating three with distilled water and dehydrated alcohol respectively Secondary, 60 DEG C of dry 12h obtain light gray presoma, after in N2750 DEG C of calcining 2h, obtain ZnS/C material in atmosphere.
2. the thick tin mud that will be directly obtained from workshop uses distillation for the influence for removing foreign ion respectively Water/washes of absolute alcohol tin mud is later centrifugated solution, cleans 3 times, is placed in drying box after 60 DEG C of dry 10h repeatedly Obtain pistac powder SnO2。
3. using mechanical attrition method dry grinding mode, ZnS/C and SnO2The mixing of 2:1 in mass ratio, ratio of grinding media to material is about 30:1, is turned Speed is 200 revs/min, and Ball-milling Time is that 10h prepares ZnS/C-SnO2Composite material.
Embodiment 7: the clay standby ZnS/C-SnO of tin is utilized2Composite material
Using zinc acetate, vulcanized sodium and DEXTROSE ANHYDROUS as raw material, the C of 2.153g is weighed4H6O4Zn·2H2O, 4.712g Na2S·9H2O and 5.454g DEXTROSE ANHYDROUS is dissolved in 150mL distilled water simultaneously after formation clear transparent solutions, moves into reaction kettle At 180 DEG C after hydro-thermal reaction 12h, centrifugation-washing-ultrasonic disperse washs precipitating three times with distilled water and dehydrated alcohol respectively, 60 DEG C of dry 12h obtain light gray presoma, after in N2750 DEG C of calcining 2h, obtain ZnS/C material in atmosphere.
The thick tin mud that will be directly obtained from workshop, for remove foreign ion influence, respectively with distilled water/ Washes of absolute alcohol tin mud is later centrifugated solution, cleans 3 times repeatedly, is placed in drying box and obtains after 60 DEG C of dry 10h Pistac powder SnO2。
Using mechanical attrition method dry grinding mode, ZnS/C and SnO2The mixing of 3:1 in mass ratio, ratio of grinding media to material is about 30:1, revolving speed It is 200 revs/min, Ball-milling Time is that 10h prepares ZnS/C-SnO2Composite material.
Embodiment 8: the clay standby ZnS/C-SnO of tin is utilized2Composite material
Using zinc acetate, vulcanized sodium and DEXTROSE ANHYDROUS as raw material, the C of 2.153g is weighed4H6O4Zn·2H2O, 4.712g Na2S·9H2O and 5.454g DEXTROSE ANHYDROUS is dissolved in 150mL distilled water simultaneously after formation clear transparent solutions, moves into reaction kettle At 180 DEG C after hydro-thermal reaction 12h, centrifugation-washing-ultrasonic disperse washs precipitating three times with distilled water and dehydrated alcohol respectively, 60 DEG C of dry 12h obtain light gray presoma, after in N2750 DEG C of calcining 2h, obtain ZnS/C material in atmosphere.
The thick tin mud that will be directly obtained from workshop, for remove foreign ion influence, respectively with distilled water/ Washes of absolute alcohol tin mud is later centrifugated solution, cleans 3 times repeatedly, is placed in drying box and obtains after 60 DEG C of dry 10h Pistac powder SnO2。
Using mechanical attrition method dry grinding mode, ZnS/C and SnO2The mixing of 4:1 in mass ratio, ratio of grinding media to material is about 30:1, revolving speed It is 200 revs/min, Ball-milling Time is that 10h prepares ZnS/C-SnO2Composite material.
It is proved by above embodiments and test result, anode material of lithium-ion battery ZnS/C- made from the method for the present invention SnO2Really it can meet the performance requirement to anode material of lithium-ion battery, there is preferable specific capacity, higher initial capacity With ideal cyclical stability, status of the sodium-ion battery in energy-storage system is promoted.
The technical concepts and features of embodiments above only to illustrate the invention, its object is to allow be familiar with technique Personage can understand the content of the present invention and implement it accordingly, it is not intended to limit the scope of the present invention, it is all according to this Equivalent change or modification made by spirit essence, should be covered by the protection scope of the present invention.

Claims (10)

1. a kind of utilize the clay standby anode material of lithium-ion battery ZnS/C-SnO of tin2Method, characterized in that it comprises:
S1: tin mud is washed, is dried, SnO is obtained2Material；
S2: one step hydro thermal method prepares ZnS/C composite material: carrying out hydro-thermal reaction by raw material of zinc salt, sulphur source and organic carbon source, instead Precipitating, drying are collected after answering, and obtain composite material precursor, composite material precursor is placed in inert atmosphere and is roasted, Obtain ZnS/C composite material；
S3: SnO prepared by step S12Material mixes in proportion with ZnS/C composite material prepared by step S2, and sodium ion is made Cell negative electrode material ZnS/C-SnO2。
2. the method according to claim 1, wherein carrying out washing to tin mud includes: distillation washing in step S1 It washs and is washed with dehydrated alcohol；And when washing, tin mud and the mixed volume ratio of distilled water or dehydrated alcohol are about 1~5:6.
3. according to the method described in claim 2, it is characterized in that, the washing includes 3 times or more, i.e., including 3 in step S1 The secondary above distillation water washing and 3 times or more dehydrated alcohol washing, distill water washing and are that either order is carried out or handed over without water washing Fork carries out.
4. according to the method described in claim 3, it is characterized in that, the drying in step S1 is at 60~80 DEG C in step S1 Lower drying, 10~12h of drying time obtain pistac powder, i.e. SnO2Material.
5. the method according to claim 1, wherein the zinc salt is zinc acetate, zinc nitrate, chlorine in step S2 Change one or more of zinc；The sulphur source is one or more of sulphur powder, vulcanized sodium, thiocarbamide；The organic carbon source is Portugal One or more of grape sugar, sucrose, starch, citric acid；The zinc salt, sulphur source, organic carbon source are soluble in water, are then transferred to Hydrothermal reaction kettle sealing reaction.
6. according to the method described in claim 5, it is characterized in that, in step S2, the temperature of the hydro-thermal reaction is 120~ 180 DEG C, 10~14h of reaction time.
7. according to the method described in claim 6, it is characterized in that, collecting precipitating after hydro-thermal reaction, so in step S2 Hydro-thermal reaction product is carried out afterwards to be centrifuged-wash-ultrasonic disperse-drying and processing, obtains composite material precursor later；Centrifugation point From the sediment of hydro-thermal reaction is obtained, washing is respectively washed 3 times or more using distilled water and dehydrated alcohol, and ultrasonic disperse is to wash Ultrasonic wave is loaded during washing, drying is the dry 10-12h at 60-80 DEG C.
8. the method according to the description of claim 7 is characterized in that composite material precursor is placed in nitrogen or argon in step S2 In gas atmosphere, in 600~900 DEG C of 2~5h of roasting, ZnS/C composite material is obtained.
9. the method according to claim 1, wherein in step S3: being prepared S1 using dry ball milling mode SnO2Material is mixed with ZnS/C composite material 1:1~4 in mass ratio prepared by S2, and ratio of grinding media to material is 20~30:1,200~800r/ Anode material of lithium-ion battery ZnS/C-SnO is made in 1~15h of ball milling under min2。
10. a kind of anode material of lithium-ion battery is made by method according to any one of claims 1 to 9.
CN201811228765.5A 2018-10-22 2018-10-22 Preparation of sodium ion battery negative electrode material ZnS/C-SnO by using tin mud2Method (2) Active CN109378458B (en)

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