CN110534727A - A kind of tin zinc double metallic composite material and preparation method thereof - Google Patents
A kind of tin zinc double metallic composite material and preparation method thereof Download PDFInfo
- Publication number
- CN110534727A CN110534727A CN201910719882.XA CN201910719882A CN110534727A CN 110534727 A CN110534727 A CN 110534727A CN 201910719882 A CN201910719882 A CN 201910719882A CN 110534727 A CN110534727 A CN 110534727A
- Authority
- CN
- China
- Prior art keywords
- metallic composite
- composite material
- preparation
- double metallic
- tin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Abstract
A kind of tin zinc double metallic composite material and preparation method thereof, the general formula of the composite material are SnxOx/ZnySy- C, preparation method are: pink salt, zinc salt and organic ligand being used to prepare Sn/Zn-MOF presoma for raw material first；Then sulphur source, carbon source and the Sn/Zn-MOF presoma is used to carry out hydro-thermal reaction for raw material,.This method is uniformly distributed zinc-base sulfide and tin-based oxide in material, improves the reversible specific capacity and electric conductivity of tin zinc double metallic composite material；Meanwhile by hydro-thermal reaction carbon source is uniformly coated, further improve the cyclical stability of battery；When selecting the SnO/ZnS-rGO of graphene content 20%, in the voltage range of 0.01 ~ 3.0V, after the circle of 1C circulation 200, specific discharge capacity is still up to 1547.7mAh/g.
Description
Technical field
The invention belongs to lithium cell cathode material fields, and in particular to a kind of tin zinc double metallic composite material and its preparation side
Method.
Background technique
Lithium ion battery has energy density height, the small, good cycle of self discharge etc. as the outstanding person in secondary cell
Advantage.As negative electrode of lithium ion battery, tin base cathode material is possible to replace biography in future due to its higher energy density
System graphite cathode, but since volume expansion easily occurs in charge and discharge process for such negative electrode material, so as to cause material powder
Change, destroys structure.Thus it is common to use material nano or the method compound with other materials are improved its performance.
The preparation of tin metal organic frame is just applied to transition metal oxide, selenides and vulcanization in recent years
Among the preparation of object negative electrode material.Beijing University of Chemical Technology, the Zhuo Bian et al. of chemical resource engineering National Key Laboratory
(Bian Z, Li A, He R, et al. Metal-organic framework-templated porous SnO/C
polyhedrons for high-performance lithium-ion batteries[J]. Electrochimica
Acta, 2018,289:389-396.), with stannous sulfate (SnSO4), terephthalic acid (TPA) (H2BDC), lithium hydroxide (LiOH)
It is raw material with n,N-Dimethylformamide (DMF), by the H of 0.012 mol2The LiOH of BDC and 0.024 mol are dissolved in 100 mL
The DMF of volume ratio 1:1 and the in the mixed solvent of deionized water, respectively stirring in water bath 2h and dropwise addition 20 simultaneously at 25 DEG C and 50 DEG C
The SnSO of the 0.25mol L-1 of mL4Aqueous solution: using terephthalic acid (TPA) as organic ligand, stannous sulfate as tin source, DMF with
The mixed solution of water makees solvent and adjusts pH value using lithium hydroxide, prepares tin metal organic frame with this control condition.Wei Si
Xiaoyu Sui of Kang Xing university et al. (Sui X, Huang X, Wu Y, et al. Organometallic
precursor-derived SnO2/Sn-reduced graphene oxide sandwiched nanocomposite
anode with superior lithium storage capacity[J]. ACS applied materials &
Interfaces, 2018,10 (31): 26170-26177.), with graphene oxide (GO), methanol, stannous chloride
(SnCl2·2H2O), 2-methylimidazole (Hmim) is raw material, and using methanol as solvent, 2-methylimidazole is prepared as organic ligand
Tin metal organic frame, and SnO is obtained by lower 650 DEG C of the calcining of argon atmosphere as presoma2/ Sn-rGO cathode material
Material, the material is in 1.6 A g-1Current density under 400 circle still keep 449 mAh g-1Highly stable circulation specific volume
Amount, has shown preferable cycle performance.Although two documents have all been successfully prepared the organic framework materials of tin metal,
Presoma is that individual metal salt is single metal organic frame prepared by raw material, and final product material is single metal oxygen
Compound or sulfide, the cycle performance and specific capacity of material are to be improved.
For the electric conductivity and cycle performance of battery for further increasing negative electrode material, researcher is usually by tin-based oxide
Sulfide material adulterates the crystal structure of the further stabilizing material of other transition metal, but other extremely difficult for realizing doping in technique
Transition metal is uniformly distributed, and the composite material for often leading to preparation cannot get a desired effect.
Summary of the invention
The technical problems to be solved by the present invention are: it is compound to overcome the deficiencies of the prior art and provide a kind of tin zinc bimetallic
Material, SnO and ZnS in the composite material are evenly distributed, and have excellent lead using negative electrode material prepared by the composite material
Electrical property and cyclic specific capacity.
The technical proposal for solving the technical problem of the invention is:
A kind of tin zinc double metallic composite material, the chemical general formula of the tin zinc double metallic composite material are SnxOx/ZnySy- C,
In, 0.5≤y≤2,0.5≤x≤2.
Preferably, the tin zinc double metallic composite material floriform appearance that leaf intersects in the form of sheets.
Preferably, 0.5≤y≤1.5；It is highly preferred that 1≤y≤1.5；It is further preferred that y=1.
Preferably, 0.5≤x≤1.5；It is highly preferred that 1≤x≤1.5；It is further preferred that x=1.
The preparation method of tin zinc double metallic composite material of the present invention, this method use pink salt, zinc salt and organic ligand first
Sn/Zn-MOF presoma is prepared for raw material；Then sulphur source, carbon source and the Sn/Zn-MOF presoma is used to carry out water for raw material
Thermal response obtains the tin zinc double metallic composite material.
Preferably, the pink salt is selected from stannous chloride and one of stannous sulfate and the hydrate of the two or a variety of；
Zinc salt is selected from one of zinc nitrate, zinc sulfate and zinc chloride and the hydrate of three or a variety of.
Preferably, the organic ligand is 2-methylimidazole, terephthalic acid (TPA), phthalic acid or 1,3,5-Benzenetricarboxylic acid.
Preferably, the sulphur source in thiocarbamide, thioacetamide, glutathione, vulcanized sodium and L-cysteine one
Kind is a variety of.
Preferably, the carbon source is selected from graphene oxide, sucrose, glucose, glycogen, cellulose, polyvinylpyrrolidone
With one of citric acid or a variety of.
Preferably, the preparation method comprising the following specific steps
(1) organic ligand solution is added into the mixed solution of pink salt and zinc salt, forms reaction solution, make tin ion and zinc ion with
Organic ligand reaction, generates precipitating, stands, and is separated by solid-liquid separation, dry, obtains the Sn/Zn-MOF presoma；
(2) it by carbon source, sulphur source and the Sn/Zn-MOF presoma is evenly dispersed obtains suspension into solvent I, is then heated to
150 ~ 190 DEG C, reaction 10 ~ for 24 hours, it after the reaction was completed, is separated by solid-liquid separation, washs, it is dry, obtain the tin zinc bimetallic composite wood
Material.
Preferably, in the amount of the substance of the organic ligand and pink salt in tin element and zinc salt Zn-ef ficiency substance the sum of amount
Ratio be 8:1.
Preferably, in the reaction solution, Sn2+And Zn2+Concentration ratio be 1:1.
Preferably, in the reaction solution, Sn2+And Zn2+Total concentration be 0.04 mol/L.
Preferably, the mixed solution is identical with the solvent in organic ligand solution, more preferably, the mixed solution
It is water with the solvent in organic ligand solution.
Preferably, the ratio between the sulphur source and the amount of substance of metallic element in the Sn/Zn-MOF presoma are 4:1.
Preferably, the mass ratio of the carbon source and the Sn/Zn-MOF presoma is 1 ~ 3:7 ~ 9, more preferably, described
The mass ratio of carbon source and the Sn/Zn-MOF presoma is 4 ~ 5:15 ~ 16.
Preferably, in the suspension, the concentration of the Sn/Zn-MOF presoma is 0.005 ~ 0.01g/mL.
Preferably, in the step (2), the temperature of the reaction is 170 ~ 180 DEG C, and the time of the reaction is 12 ~ 14
h。
The beneficial effects of the present invention are:
(1) preparation method of the invention carries out the preparation of presoma using the bimetal salt of tin and zinc, and prepares novel tin
Zinc bimetallic organic frame prepares SnO/ZnS-rGO negative electrode active material using hydro-thermal method, and the negative electrode material of preparation is followed
Ring performance and specific capacity are above similar document；Your method raw material of the present invention is easy to get, easy to operate, is advantageously implemented industrialization
Production；
(2) preparation method of the invention realizes in tin-based oxide material zinc-base sulfide to tin by preparing Sn/Zn-MOF
The part of base oxide replaces to obtain tin zinc double metallic composite material, but also wherein zinc-base sulfide and tin-based oxide are able to
It is uniformly distributed, and then improves the reversible specific capacity and electric conductivity of tin zinc double metallic composite material；Meanwhile by using sulphur source,
The hydro-thermal reaction of carbon source and Sn/Zn-MOF further improves the cyclical stability of battery so that carbon source uniformly coats；It is elected
When with the SnO/ZnS-rGO of graphene content 20%, in the voltage range of 0.01 ~ 3.0V, after the circle of 1C circulation 200,
Specific discharge capacity is up to 1547.7mAh/g.
Detailed description of the invention
Fig. 1 is the SEM figure of Sn/Zn-MOF obtained by 1 step of embodiment (1), wherein the SEM that left side is low range schemes, right side
For corresponding high magnification SEM figure；
Fig. 2 is the SEM figure of SnO/ZnS-rGO prepared by embodiment 1；
Fig. 3 is the XRD diagram of the SnO/ZnS-rGO of embodiment 1-4 preparation；
Fig. 4 is the cycle performance of the battery assembled using the negative electrode material of the preparation of SnO/ZnS-rGO made from embodiment 1-4
Figure.
Specific embodiment
The present invention is further detailed with attached drawing with reference to embodiments.
Embodiment 1
The present embodiment the following steps are included:
(1) the zinc nitrate hexahydrate 0.2975g for weighing two the hydrated stannous chloride 0.2257g, 0.001mol of 0.001 mol is added
Into 10 mL deionized waters, the disperse system of homogeneous, as mixed solution are obtained；Weigh the 2-methylimidazole of 0.016 mol
1.3136g is added into 15ml deionized water, through ultrasound to being completely dissolved, as organic ligand solution；Mixed solution is placed in
In 25 DEG C of water-bath, it is rapidly added organic ligand solution after turning speed to 800 r/min, forms reaction solution, then persistently stir
Constant temperature 5min；12h is stood after reaction, is dried 4h after being centrifuged, washing 3 times in 120 DEG C of air dry oven, is just made
Sn/Zn-MOF presoma；
(2) by the 5g L of 35 mL deionized waters and 15 mL-1Graphene oxide water solution mixes, and ultrasonic half an hour makes it
It being thoroughly mixed, 0.301gSn/Zn-MOF presoma is added, ultrasonic 1-2 h simultaneously stirs 0.5 h, Sn/Zn-MOF is made to be uniformly dispersed,
It is subsequently poured into 0.27 g (3.6 mmol) thioacetamide dissolved with 10 mL water, 0.5h is stirred for, obtains suspension, then
Suspension is poured into 100 mL reaction kettles, 12 h of hydro-thermal reaction, is centrifuged in draught cupboard later at 180 DEG C, is spent
Ion water washing, and carry out cold dry, obtain the tin zinc double metallic composite material, the as SnO/ZnS- of graphene content 20%
rGO。
To Sn/Zn-MOF presoma made from the present embodiment step (1), and final graphene content 20% obtained
SnO/ZnS-rGO product carries out electron-microscope scanning, and result is as illustrated in fig. 1 and 2, and Sn/Zn-MOF has short grained sheet in surface
Leaf pattern, the SnO/ZnS-rGO floriform appearance that leaf intersects in the form of sheets, graphene coated is on the surface of material.
Embodiment 2
This example the following steps are included:
(1) the zinc nitrate hexahydrate 0.2975g for weighing two the hydrated stannous chloride 0.2257g, 0.001mol of 0.001 mol is added
The disperse system of homogeneous, as mixed solution are obtained into 10 mL deionized waters；Weigh the 2-methylimidazole of 0.016 mol
1.3136g is added into 15mL deionized water, arrives organic ligand solution to being completely dissolved through ultrasound；Mixed solution is set
In 25 DEG C of water-bath, it is rapidly added organic ligand solution after turning speed to 800 r/min, forms reaction solution, then persistently stir
Mix constant temperature 5min；After reaction, 12h is stood, dries 4h after being centrifuged, washing 3 times in 120 DEG C of air dry oven, just
Sn/Zn-MOF presoma is made；
(2) by the 5g L of 44 mL deionized waters and 6 mL-1Graphene oxide water solution mixes, and ultrasonic half an hour keeps its complete
Full mixing, is added 0.301g presoma, and ultrasonic 1-2 h simultaneously stirs 0.5 h, so that Sn/Zn-MOF is uniformly dispersed, pour into 10 at this time
0.27 g (3.6 mmol) thioacetamide of mL water dissolution is stirred for 0.5h and obtains suspension, and suspension is then poured into 100
In mL reaction kettle, 12 h of hydro-thermal reaction at 180 DEG C carries out centrifugation deionized water washing in draught cupboard later, and carries out cold
It is dry, the tin zinc double metallic composite material is obtained, the SnO/ZnS-rGO of graphene content 10% is denoted as.
Embodiment 3
The present embodiment the following steps are included:
(1) the zinc nitrate hexahydrate 0.2975g for weighing two the hydrated stannous chloride 0.2257g, 0.001mol of 0.001 mol is added
Into 10 mL deionized waters, homogenous disperse system, as mixed solution are obtained；Weigh the 2-methylimidazole of 0.016 mol
1.3136g is added into 15ml deionized water, through ultrasound to being completely dissolved, obtains organic ligand solution；Mixed solution is placed in
In 25 DEG C of water-bath, it is rapidly added organic ligand solution after turning speed to 800 r/min, forms reaction solution, then persistently stir
Constant temperature 5min；After reaction, 12h is stood, 4h is dried after being centrifuged, washing 3 times in 120 DEG C of air dry oven, just makes
Obtain Sn/Zn-MOF presoma；
(2) by the 5g L of 40 mL deionized waters and 10 mL-1Graphene oxide water solution mixes, and ultrasonic half an hour makes it
It is thoroughly mixed, 0.301g presoma is added, ultrasonic 1-2 h simultaneously stirs 0.5 h, so that Sn/Zn-MOF is uniformly dispersed, be subsequently poured into 10
0.27 g (3.6 mmol) thioacetamide of mL water dissolution is stirred for 0.5h and obtains suspension；Suspension is then poured into 100
In mL reaction kettle, 12 h of hydro-thermal reaction at 180 DEG C.Centrifugation deionized water washing is carried out in draught cupboard later, and is carried out cold
It is dry, the tin zinc double metallic composite material is obtained, the SnO/ZnS-rGO of graphene content 15% is denoted as.
Embodiment 4
The present embodiment the following steps are included:
(1) the zinc nitrate hexahydrate 0.2975g for weighing two the hydrated stannous chloride 0.2257g, 0.001mol of 0.001 mol is added
Into 10 mL deionized waters, the disperse system of homogeneous, as mixed solution are obtained；Weigh the 2-methylimidazole of 0.016 mol
1.3136g is added into 15ml deionized water, through ultrasound to being completely dissolved, obtains organic ligand solution；Mixed solution is placed in
In 25 DEG C of water-bath, it is rapidly added organic ligand solution after turning speed to 800 r/min, forms reaction solution, then persistently stir
Constant temperature 5min；After reaction, 12h is stood, 4h is dried after being centrifuged, washing 3 times in 120 DEG C of air dry oven, just makes
Obtain Sn/Zn-MOF presoma；
(2) by the 5g L of 30 mL deionized waters and 20 mL-1Graphene oxide water solution mixes, and ultrasonic half an hour makes it
It is thoroughly mixed, 0.301g presoma is added, ultrasonic 1-2 h simultaneously stirs 0.5 h, so that Sn/Zn-MOF is uniformly dispersed, pour into 10 at this time
0.27 g (3.6 mmol) thioacetamide of mL water dissolution is stirred for 0.5h and obtains suspension；.Then suspension is poured into
In 100 mL reaction kettles, 12 h of hydro-thermal reaction at 180 DEG C.Centrifugation deionized water washing is carried out in draught cupboard later, is gone forward side by side
Row is cold dry.Just the SnO/ZnS-rGO material of graphene content 25% is made.
Inventor successively carries out X-ray diffraction to tin zinc double metallic composite material prepared by embodiment 1-4, obtains such as Fig. 3
Shown in XRD diagram, referring to Fig. 3 it is found that the material that embodiment 1-4 is obtained is SnO(JCPDS PDF#78-1913) and ZnS
The composite material of (JCPDS PDF#12-0688).
Negative electrode material is prepared using tin zinc double metallic composite material prepared by embodiment 1 ~ 4, and uses the negative electrode material system
Standby cathode is assembled into battery, and universal process is as follows:
(1) preparation of negative electrode material: tin zinc double metallic composite material in mass ratio: carbon black: PVDF=7:2:1 weighs raw material respectively,
Then mortar is added, is added few drops of NMP after grinding uniformly, until immobilising semi liquid state cathode material is presented；
(2) preparation of cathode: interception copper foil, by dehydrated alcohol by its it is smooth be layered on glass plate, choose 75 μ m thicks
Smear；It is in long strip to be placed on copper foil with the cathode material on spoon scraping mortar, then uniformly applied with 75 μm of smear machine
On copper foil；Copper foil after smear is placed in 80 DEG C of vacuum drying oven, is taken out by 5h or so and is cut anode foil；Use pan paper
Pad the upper and lower sides in copper foil respectively, prevent dust pollution pole piece interference experiment as a result, after with tablet press machine cut copper foil, be less than
The one side of circular diaphragm has the round anode foil of tin zinc double metallic composite material, and every load capacity is about 0.4mg ~ 0.6mg；
(3) assembling of battery: obtained round anode foil, diaphragm, anode cover negative electrode casing and tweezers, disposable dropper etc. are put
It is placed in 60 DEG C of convection ovens, moisture is removed in drying.It then places it in glove box transitional storehouse, vacuumizes repeatedly 3 times, guarantee
Remove oxygen and a small amount of water.A series for articles is placed in glove box from transitional storehouse, starts the assembling of button cell.First
Anode cover is placed on dust-free paper, round cathode copper sheet is placed on to the center of anode cover, is instilled using disposable dropper few
Measure electrolyte (1 mol L-1 LiPF6Ethylene carbonate: dimethyl carbonate: diethyl carbonate=1:1:1), then will be slightly larger than
The diaphragm of pole piece is slowly placed on pole piece, and bubble is discharged.More smooth lithium piece is taken out later places it in diaphragm center,
Again with sequentially covering gasket, spring leaf and anode cover, and anode cover is pressed lightly on tweezers after loading onto anode cover, makes it uniformly
It covers on spring leaf.Then button cell is pressed from both sides to hydraulic press with plastic tweezer, multiple swinging handle is compacted it sufficiently.Most
Afterwards with the electrolyte of paper handkerchief wiping button cell surface residual, stand for 24 hours to electro-chemical test.
The tin zinc double metallic composite material assembled battery successively prepared using embodiment 1 ~ 4, and electro-chemical test is carried out, electricity
The result of test chemical is as shown in figure 4, as can be seen from FIG. 4, the SnO/ZnS material of 20% mass fraction of graphene cladding has most
Good first charge-discharge specific capacity, and there is optimal cycle performance, through 1 C circulation in the voltage range of 0.01 ~ 3.0 V
Its specific discharge capacity is 1547.7 mAh/g after 200 circles.Graphene mass fraction is respectively 10%, 15%, 20%, 25% SnO/
ZnS-rGO material, in 1 A g-1Current density under, first charge-discharge capacity is respectively 987.4 mAh g-1、1022.4 mAh
g-1、1590.7 mAh g-1、1587.2 mAh g-1, 825.7 mAh g are kept respectively after the circle of circulation 200-1、853.9 mAh
g-1、1547.7 mAh g-1、1296.7 mAh g-1Height ratio capacity.By Fig. 4 analysis it is found that when graphene content is lower than 20%,
Cycle performance is poor；And when graphene content is higher than 20%, since graphene content increases, charge/discharge capacity is reduced, therefore by
The SnO/ZnS-rGO material of 20% graphene content of map analysis is the optimal material of chemical property.When charge and discharge cycles are to centainly
After enclosing number, due to activating completely, charge/discharge capacity is in slow rise trend.
Embodiment 5
The present embodiment the following steps are included:
(1) the zinc nitrate hexahydrate 0.2975g for weighing two the hydrated stannous chloride 0.2257g, 0.001mol of 0.001 mol is added
Into 10 mL deionized waters, the disperse system of homogeneous, as mixed solution are obtained；Weigh the 2-methylimidazole of 0.016 mol
1.3136g is added into 15ml deionized water, through ultrasound to being completely dissolved, obtains organic ligand solution；Mixed solution is placed in
In 25 DEG C of water-bath, it is rapidly added organic ligand solution after turning speed to 800 r/min, forms reaction solution, then persistently stir
Constant temperature 5min；12h is stood after reaction, is dried 4h after being centrifuged, washing 3 times in 120 DEG C of air dry oven, is just made
Sn/Zn-MOF presoma；
(3) by the 5g L of 35 mL deionized waters and 15 mL-1Graphene oxide water solution mixes, and ultrasonic half an hour makes it
It is thoroughly mixed, 0.301g presoma, then ultrasound 1-2 h and 0.5 h of stirring is added, so that Sn/Zn-MOF is uniformly dispersed, pours at this time
0.27 g (3.6 mmol) thioacetamide of 10 mL water dissolution is stirred for 0.5h and obtains suspension, then pours into suspension
In 100 mL reaction kettles, 12 h of hydro-thermal reaction at 170 DEG C carries out centrifugation deionized water washing in draught cupboard later, goes forward side by side
Row it is cold it is dry obtain the tin zinc double metallic composite material, be denoted as the SnO/ZnS-rGO material of graphene content 20%.
Embodiment 6
The present embodiment the following steps are included:
(1) the zinc nitrate hexahydrate 0.2975g for weighing two the hydrated stannous chloride 0.2257g, 0.001mol of 0.001 mol is added
Into 10 mL deionized waters, the disperse system of homogeneous, as mixed solution are obtained；Weigh the 2-methylimidazole of 0.016 mol
1.3136g is added into 15ml deionized water, through ultrasound to being completely dissolved, obtains organic ligand solution；Mixed solution is placed in
In 25 DEG C of water-bath, it is rapidly added organic ligand solution after turning speed to 800 r/min, forms reaction solution, then persistently stir
Constant temperature 5min；12h is stood after reaction, is dried 4h after being centrifuged, washing 3 times in 120 DEG C of air dry oven, is just made
Sn/Zn-MOF presoma；
(2) by the 5g L of 35 mL deionized waters and 15 mL-1Graphene oxide water solution mixes, and ultrasonic half an hour makes it
It is thoroughly mixed, 0.301g presoma, then ultrasound 1-2 h and 0.5 h of stirring is added, so that Sn/Zn-MOF is uniformly dispersed, pours at this time
0.27 g (3.6 mmol) thioacetamide of 10 mL water dissolution is stirred for 0.5h and obtains suspension；Then suspension is poured into
In 100 mL reaction kettles, 14 h of hydro-thermal reaction at 180 DEG C carries out centrifugation deionized water washing in draught cupboard later, goes forward side by side
Row is cold dry, obtains the tin zinc double metallic composite material, is denoted as the SnO/ZnS-rGO material of graphene content 20%.
Above said content is only the basic explanation under present inventive concept, and what technical solution according to the present invention was done appoints
What equivalent transformation, is within the scope of protection of the invention.
Claims (10)
1. a kind of tin zinc double metallic composite material, which is characterized in that the chemical general formula of the tin zinc double metallic composite material is
SnxOx/ZnySy- C, wherein 0.5≤y≤2,0.5≤x≤2.
2. tin zinc double metallic composite material according to claim 1, which is characterized in that the tin zinc double metallic composite material
The floriform appearance that leaf intersects in the form of sheets；Preferably, 0.5≤y≤1.5,0.5≤x≤1.5；It is highly preferred that 1≤y≤1.5,
1≤x≤1.5；It is further preferred that x=1, y=1.
3. a kind of preparation method of the tin zinc double metallic composite material as described in claims 1 or 2, which is characterized in that adopt first
It is raw material preparation Sn/Zn-MOF presoma with pink salt, zinc salt and organic ligand；Then sulphur source, carbon source and the Sn/Zn- are used
MOF presoma is that raw material carries out hydro-thermal reaction, obtains the tin zinc double metallic composite material.
4. the preparation method of tin zinc double metallic composite material according to claim 3, which is characterized in that the pink salt is selected from
One of stannous chloride and stannous sulfate and the hydrate of the two are a variety of；The zinc salt be selected from zinc nitrate, zinc sulfate and
One of zinc chloride and the hydrate of three are a variety of；Preferably, the organic ligand is 2-methylimidazole, terephthaldehyde
Acid, phthalic acid or 1,3,5-Benzenetricarboxylic acid.
5. the preparation method of tin zinc double metallic composite material according to claim 3 or 4, which is characterized in that the sulphur source
Selected from one of thiocarbamide, thioacetamide, glutathione, vulcanized sodium and L-cysteine or a variety of；Preferably, the carbon source
Selected from one of graphene oxide, sucrose, glucose, glycogen, cellulose, polyvinylpyrrolidone and citric acid or a variety of.
6. according to the preparation method of the described in any item tin zinc double metallic composite materials of claim 3-5, which is characterized in that including
Step in detail below:
(1) organic ligand solution is added into the mixed solution of pink salt and zinc salt, forms reaction solution, make tin ion and zinc ion with
Organic ligand reaction, generates precipitating, stands, and is separated by solid-liquid separation, dry, obtains the Sn/Zn-MOF presoma；
(2) carbon source, sulphur source and the Sn/Zn-MOF presoma is evenly dispersed into solvent I, suspension is obtained, is then heated
To 150 ~ 190 DEG C, reaction 10 ~ for 24 hours, it after the reaction was completed, is separated by solid-liquid separation, washs, it is dry, obtain the tin zinc bimetallic composite wood
Material.
7. the preparation method of tin zinc double metallic composite material according to claim 6, which is characterized in that the organic ligand
Substance amount and pink salt in tin element and zinc salt the ratio of the sum of amount of Zn-ef ficiency substance be 8:1；Preferably, the reaction solution
In, Sn2+And Zn2+Concentration ratio be 1:1；Preferably, in the reaction solution, Sn2+And Zn2+Total concentration be 0.04 mol/L；It is excellent
Choosing, the mixed solution is identical with the solvent in organic ligand solution；More preferably, the mixed solution and organic ligand
Solvent in solution is water.
8. according to the preparation method of the described in any item tin zinc double metallic composite materials of claim 3-7, which is characterized in that described
The ratio between amount of substance of metallic element is 4:1 in sulphur source and the Sn/Zn-MOF presoma；Preferably, the carbon source with it is described
The mass ratio of Sn/Zn-MOF presoma is 1 ~ 3:7 ~ 9, more preferably, the matter of the carbon source and the Sn/Zn-MOF presoma
Amount is than being 4 ~ 5:15 ~ 16.
9. according to the preparation method of the described in any item tin zinc double metallic composite materials of claim 6-8, which is characterized in that described
In step (2), the temperature of the reaction is 170 ~ 180 DEG C；Preferably, in the suspension, the Sn/Zn-MOF presoma
Concentration is 0.005 ~ 0.01g/mL.
10. according to the preparation method of the described in any item tin zinc double metallic composite materials of claim 6-9, which is characterized in that institute
It states in step (2), the time of the reaction is 12 ~ 14 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910719882.XA CN110534727B (en) | 2019-08-06 | 2019-08-06 | Tin-zinc bimetal composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910719882.XA CN110534727B (en) | 2019-08-06 | 2019-08-06 | Tin-zinc bimetal composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110534727A true CN110534727A (en) | 2019-12-03 |
| CN110534727B CN110534727B (en) | 2021-04-02 |
Family
ID=68661524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910719882.XA Active CN110534727B (en) | 2019-08-06 | 2019-08-06 | Tin-zinc bimetal composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110534727B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111384387A (en) * | 2020-06-01 | 2020-07-07 | 杭州德飙新能源设备有限公司 | Lithium ion battery and preparation method thereof |
| CN111900346A (en) * | 2020-07-13 | 2020-11-06 | 滁州学院 | Carbon-coated tin dioxide/zinc sulfide hollow cubic nano composite material, preparation method thereof, lithium ion battery cathode and battery |
| CN113036113A (en) * | 2021-03-11 | 2021-06-25 | 东北大学 | Doped BaSO4Sodium ion battery cathode material and preparation method thereof |
| CN115259210A (en) * | 2022-08-29 | 2022-11-01 | 北京化工大学 | MOF-derived SnO 2 Preparation method and application of |
| CN115434041A (en) * | 2022-08-30 | 2022-12-06 | 华中科技大学 | Tin-doped porous carbon fiber material for MOF (metal-organic framework) pore in-situ reaction and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948105A (en) * | 2016-05-06 | 2016-09-21 | 西北大学 | SnO2/ZnO nano composite material and preparation method thereof |
| CN107803207A (en) * | 2017-10-18 | 2018-03-16 | 中南大学 | A kind of carbon-based double metallic composite material, preparation and its application |
| CN109694101A (en) * | 2019-02-14 | 2019-04-30 | 西北大学 | A kind of SnO2@ZnO nano composite material and preparation method |
-
2019
- 2019-08-06 CN CN201910719882.XA patent/CN110534727B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948105A (en) * | 2016-05-06 | 2016-09-21 | 西北大学 | SnO2/ZnO nano composite material and preparation method thereof |
| CN107803207A (en) * | 2017-10-18 | 2018-03-16 | 中南大学 | A kind of carbon-based double metallic composite material, preparation and its application |
| CN109694101A (en) * | 2019-02-14 | 2019-04-30 | 西北大学 | A kind of SnO2@ZnO nano composite material and preparation method |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111384387A (en) * | 2020-06-01 | 2020-07-07 | 杭州德飙新能源设备有限公司 | Lithium ion battery and preparation method thereof |
| CN111900346A (en) * | 2020-07-13 | 2020-11-06 | 滁州学院 | Carbon-coated tin dioxide/zinc sulfide hollow cubic nano composite material, preparation method thereof, lithium ion battery cathode and battery |
| CN111900346B (en) * | 2020-07-13 | 2022-05-13 | 滁州学院 | Carbon-coated tin dioxide/zinc sulfide hollow cubic nano composite material, preparation method thereof, lithium ion battery cathode and battery |
| CN113036113A (en) * | 2021-03-11 | 2021-06-25 | 东北大学 | Doped BaSO4Sodium ion battery cathode material and preparation method thereof |
| CN115259210A (en) * | 2022-08-29 | 2022-11-01 | 北京化工大学 | MOF-derived SnO 2 Preparation method and application of |
| CN115259210B (en) * | 2022-08-29 | 2024-02-02 | 北京化工大学 | MOF-derived SnO 2 Preparation method and application of (C) |
| CN115434041A (en) * | 2022-08-30 | 2022-12-06 | 华中科技大学 | Tin-doped porous carbon fiber material for MOF (metal-organic framework) pore in-situ reaction and preparation method and application thereof |
| CN115434041B (en) * | 2022-08-30 | 2023-12-01 | 华中科技大学 | Tin-doped porous carbon fiber material with in-situ reaction in MOF pores, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110534727B (en) | 2021-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110534727A (en) | A kind of tin zinc double metallic composite material and preparation method thereof | |
| CN107359335B (en) | Nickel-cobalt lithium manganate cathode material and its preparation method and application | |
| CN103456936B (en) | Sodium ion secondary battery and the preparation method of layered titanate active substance, electrode material, both positive and negative polarity and active substance | |
| CN107069020A (en) | A kind of preparation method of lithium ion battery nickel doping vanadic anhydride nano-sheet positive electrode | |
| CN109980272A (en) | A kind of Al doping sheet LLZO composite solid electrolyte and its preparation method and application | |
| CN106673075A (en) | Modified O3 type layered cathode material of sodium-ion battery, and preparation method and application thereof | |
| CN106099052A (en) | A kind of carbon cladding SnO2hollow nanospheres composite and preparation method thereof | |
| CN110459798A (en) | The sulfide solid electrolyte and preparation method and solid state battery of core-shell structure | |
| CN108807964B (en) | Coating method and application of nickel-cobalt-aluminum ternary cathode material | |
| CN108598561A (en) | A kind of quasi- solid lithium ion conducting electrolyte and its preparation method and application | |
| CN108232142A (en) | A kind of zinc sulphide/graphene composite material, preparation method and application | |
| CN105244492A (en) | Cathode material for boracic lithium ion battery and preparation method thereof | |
| CN108963211A (en) | A kind of titanium carbide load stannous sulfide composite negative pole material | |
| CN102683665B (en) | Lithium-vanadium oxide over-long nano wire and preparation method and application thereof | |
| CN109167050A (en) | The production method of inexpensive 551530 type tertiary cathode material of high capacity | |
| CN110010878A (en) | The porous carbon coating Co of N doping3O4Composite nano materials, preparation method and applications | |
| CN110980673B (en) | Metal phosphide, preparation method thereof and application thereof in super capacitor | |
| CN105489874A (en) | Stannic oxide nanoparticles with high electrical property and preparation method therefor | |
| CN110078121A (en) | A kind of preparation method and application of Magnesium ion battery vanadic anhydride positive electrode | |
| CN108615612A (en) | A kind of flower-shaped cobaltosic oxide-graphene composite material and preparation method thereof | |
| CN107706366A (en) | A kind of positive electrode of indium oxide or tin-doped indium oxide cladding and preparation method thereof | |
| CN107895813A (en) | A kind of preparation method of high conductance lithium ion solid electrolyte | |
| CN107104248B (en) | A kind of potassium/sodium-ion battery is with opening frame fluoride positive electrode and preparation method thereof | |
| CN105304890A (en) | Cathode material for silicon-containing lithium ion battery and preparation method for cathode material | |
| CN109037632A (en) | A kind of nano lithium titanate composite material and preparation method, lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |