CN108807907A - A kind of method that one-step method prepares the spherical tin monoxide of particles self assemble/stannic oxide anode material of lithium-ion battery - Google Patents
A kind of method that one-step method prepares the spherical tin monoxide of particles self assemble/stannic oxide anode material of lithium-ion battery Download PDFInfo
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Abstract
The invention discloses a kind of methods that one-step method prepares the spherical tin monoxide of particles self assemble/stannic oxide anode material of lithium-ion battery, and thiocarbamide is dissolved in absolute ethyl alcohol first, is configured to solution A；Then citric acid is added in solution A until forming solution B after being completely dissolved under stirring；Then under stirring according to elemental mole ratios nSn:nS=(0.5~2.0):(0.9~3.0) weighs SnCl2·2H2O is dissolved in above-mentioned solution B and forms solution C；Then solution C is subjected to homogeneous hydro-thermal reaction, obtains presoma after reaction；Presoma is finally distinguished into centrifuge washing several times through deionized water and absolute ethyl alcohol, then vacuum drying obtains the spherical tin monoxide of particles self assemble/stannic oxide anode material of lithium-ion battery.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium ion battery negative material, and in particular to a kind of one-step method prepares particle
The method of the spherical tin monoxide of self assembly/stannic oxide anode material of lithium-ion battery.
Background technology
Energy and environment problem is two hang-ups that mankind nowadays social sustainable development faces, and with scarcity of resources
Consumption with the getting worse of problem of environmental pollution, traditional fossil energy rises year by year and the caused environmental pollution of its burning
Growing day by day, resulting resource and environment pressure forces people to accelerate cleaning, renewable energy utilization and exploitation, and uses
It is most effective so far with exploitation secondary rechargeable battery, can most solves the energy and a kind of necessary mode of environmental crisis.Wherein,
Sodium-ion battery has rich reserves, that cheap, environmental-friendly, safety is good etc. is excellent as a kind of electrochemical energy storage energy
Point.And it is compared with lithium ion battery, there is relatively good chemical property and the electrochemistry similar with lithium ion battery
Behavior so that it is expected to replace lithium ion battery in energy storage field, and will possess market competition than lithium ion battery bigger
Advantage.But the ionic radius (r=0.113nm) of sodium ion it is about bigger by 30% than the ionic radius of lithium ion (r=0.076nm) with
On, it is difficult to realize that the embedding dealkylation reaction of reversible electrochemistry, insertion-abjection process easily cause collapsing for host lattice structure, lead to material
The cycle performance of material, high rate performance and electrochemical utilization rate performance are poor, and therefore, finding suitable embedding sode cell material has one
Fixed difficulty.
Tin monoxide has two kinds of crystal structures of tetragonal crystal system and rhombic system.Its lattice of the tin monoxide of tetragonal crystal system is normal
Number a=b=0.3803nm, c=0.4838nm, c/a=1.27.Contain 2 basic units, all oxygen atoms in each structure cell
All it is of equal value.Tin monoxide is layer structure, and 1 tin atom and 4 oxygen atoms form a square pyramid knot
Structure, tin atom are in vertex, and bottom is 4 oxygen atoms.All it is 0.222nm with a distance from all oxygen atoms nearest from tin atom,
Each oxonium ion is surrounded by four tin ions.Tin monoxide has superior stratiform as a kind of important tin-based composites
Structure, low cost, high theoretical capacity (875mAhg-1), it is considered to be most one of the negative material of application prospect.But
Be its generated during charge and discharge cycles larger volume expansion make its structure destroy and electrode dusting, eventually lead to it
Capacity attenuation is too fast；And low electric conductivity limits its application and development as electrode material.
Since granule-morphology may also can affect to the chemical property of sample, particle is smaller, specific surface
Product is bigger, then contact of the material with electrolyte is better, Li+Migration distance can also shorten, be more advantageous to sodium-ion battery in this way
The promotion of negative material high rate performance.Currently, according to the document reported, the main method for preparing tin monoxide/tin oxide has
Method of electrostatic spinning [Cho J S, Kang Y C.Nanofibers Comprising Yolk-Shell Sn@void@SnO/SnO2
and Hollow SnO/SnO2 and SnO2 Nanospheres via the Kirkendall Diffusion Effect
and Their Electrochemical Properties[J].Small,2015,11(36):4673-4681.].Journal
of Nanoengineering&Nanomanufacturing,2015,5(3):210-215.]；Solid phase method [Santhi K, Rani
C,Karuppuchamy S.Synthesis and characterization of a novel SnO/SnO2 hybrid
photocatalyst[J].Journal of Alloys&Compounds,2016,662(40):102-107.] etc..And electrostatic
Yarn spinning productivity is unstable, and inefficiency, can only there is 0.1g/h~1g/h per hour, to its industrialization, scale and nanometer
The extensive use of fibrous material causes huge obstruction, cannot meet demand of traditional market to the dosage of nanofiber, solid phase
Reaction method has many advantages, such as not need that solvent, equipment is simple and easy control of reaction conditions, but is carried out in solid phase due to reacting,
Usually reaction is not thorough, and yield is relatively low.
Invention content
The purpose of the present invention is to provide a kind of one-step method prepare the spherical tin monoxide of particles self assemble/stannic oxide sodium from
The method of sub- cell negative electrode material, to overcome the problems of the above-mentioned prior art, tin monoxide/tin oxide prepared by the present invention
Anode material of lithium-ion battery is chondritic, and average diameter size is about 500nm~1um, and manufacturing cost is low, manufacturing cycle
Short, pattern is relatively uniform.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of one-step method prepares the side of the spherical tin monoxide of particles self assemble/stannic oxide anode material of lithium-ion battery
Method includes the following steps：
Step 1：Thiocarbamide is dissolved in absolute ethyl alcohol, solution A is configured to；Then citric acid is added under stirring
Until forming solution B after being completely dissolved in solution A；
Step 2：Under stirring according to elemental mole ratios nSn:nS=(0.5~2.0):(0.9~3.0) weighs
SnCl2·2H2O is dissolved in above-mentioned solution B and forms solution C；
Step 3：Solution C is subjected to homogeneous hydro-thermal reaction, obtains presoma after reaction；
Step 4：Presoma is distinguished into centrifuge washing several times through deionized water and absolute ethyl alcohol, then vacuum drying is
Obtain the spherical tin monoxide of particles self assemble/stannic oxide anode material of lithium-ion battery.
Further, in step 1 solution A a concentration of 0.13~0.50mol/L.
Further, in step 1 in solution B citric acid a concentration of 0.01~0.05mol/L.
Further, homogeneous hydro-thermal reaction is specially in step 3：Solution C is put into homogeneous hydrothermal reaction kettle sealing, is filled out
It fills than controlling 40%~60%, is put into homogeneous hydro-thermal reaction instrument and is reacted.
Further, the temperature of homogeneous hydro-thermal reaction is 160~200 DEG C, and the time is 16~20h.
Further, presoma is distinguished into centrifuge washing 3 times through deionized water and absolute ethyl alcohol in step 4.
Further, vacuum drying temperature is 60 DEG C in step 4, time 12h.
Compared with prior art, the present invention has technique effect beneficial below：
Tin monoxide/tin oxide anode material of lithium-ion battery prepared by the method for the present invention is chondritic, average diameter
Size is about 500nm~1um, and manufacturing cost is low, short preparation period, and pattern is relatively uniform.Moreover, by controlling response parameter
Spherical tin monoxide/tin oxide sode cell negative material is obtained, larger specific surface area increases the machine with electrolyte contacts
It can be conducive to the migration of sodium ion with reactivity site, and alleviate the volume change in charge and discharge process, be conducive to improve
The chemical property of material.Moreover, in 100mAg-1Under current density, discharge capacity 1433.5mAhg for the first time-1, cycle 10
Circle, capacity can reach 841.5mAhg-1, there is higher high rate performance under high current density.
Compare from preparation method, solvent-thermal method has simple for process, short preparation period and easy control of reaction conditions
Characteristic can be controlled the composition of the process and pattern size, object phase of reaction using different temperature, can be obtained at a suitable temperature
To different object phase compositions and special structure and morphology.The difference of object phase and appearance structure has the performance of material larger shadow
It rings, in addition, solvent-thermal method has, reaction rate is very fast, fully thorough etc. advantages of reaction, and the reaction that it avoids conventional method is difficult
The shortcomings of to carry out with difficult to control, high energy consumption, low yield and complex process.
The stannic oxide that the present invention uses has two kinds of crystal knots of rutile structure and orthorhombic structure of tetragonal crystal system
Structure.Wherein, orthogonal whisker structure (a=0.4714nm, b=0.5727nm, c=0.5210nm) is highly unstable, general only to exist
Exist under high temperature.Therefore, it is most common and it is most commonly used be tetragonal crystal system rutile structure.The rutile structure of tetragonal crystal system
Tin oxide, lattice constant a=b=0.4737nm, c=0.3186nm, c/a=0.672.Contain 2 oxidations in each plane
Tin molecule, wherein each Sn atoms are located at the octahedral center of approximation being made of 6 O atoms, and each O atom also is located at 3
The center of the former molecular equilateral triangles of a Sn.Also, stannic oxide has relatively high theoretical capacity (782mAhg-1),
And this layer structure is conducive to the insertion and abjection of sodium ion.Pass through, the Neng Gouhuan compound with stannic oxide by tin monoxide
Solve Li+Volume expansion when deintercalation process, improves the cycle performance of electrode material, and enhances the electric conductivity of negative material, from
And improve its chemical property.
Description of the drawings
Fig. 1 is the spherical tin monoxide of particles self assemble/stannic oxide sodium-ion battery cathode material prepared by example 2 of the present invention
The XRD diagram of material；
Fig. 2 is the spherical tin monoxide of particles self assemble/stannic oxide anode material of lithium-ion battery prepared by example 2 of the present invention
SEM figure；
Fig. 3 is that the particle prepared by example 2 of the present invention assembles spherical tin monoxide/stannic oxide anode material of lithium-ion battery
High rate performance figure
Specific implementation mode
Embodiments of the present invention are described in further detail below：
A kind of one-step method prepares the side of the spherical tin monoxide of particles self assemble/stannic oxide anode material of lithium-ion battery
Method includes the following steps：
1) thiocarbamide (TU) is dissolved in absolute ethyl alcohol, the solution A of a concentration of 0.13~0.50mol/L is configured to, in magnetic force
Citric acid is added in solution A until be completely dissolved to form solution B under stirring action, makes a concentration of of citric acid in solution B
0.01~0.05mol/L；
2) according to elemental mole ratios n under magnetic agitation effectSn:nS=(0.5~2.0):(0.9~3.0) is by SnCl2·
2H2O is dissolved in above-mentioned solution B, until being completely dissolved into solution C；
3) solution C is put into homogeneous hydrothermal reaction kettle to seal, packing ratio is controlled 40%~60%, and it is anti-to be put into homogeneous hydro-thermal
Ying Yi, at 160~200 DEG C, the reaction time controls in 16~20h for reaction temperature control；
4) it waits for after reaction, taking out presoma, distinguishes centrifuge washing 3 times through deionized water and absolute ethyl alcohol, obtain black
Color presoma is dried in vacuo 12h at a temperature of 60 DEG C and obtains the spherical tin monoxide of particles self assemble/stannic oxide sodium ion electricity
Pond negative material.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
1) thiocarbamide (TU) is dissolved in absolute ethyl alcohol, is configured to the solution A of a concentration of 0.13mol/L, made in magnetic agitation
Citric acid is added in above-mentioned solution A until be completely dissolved to form solution B with lower, makes a concentration of of citric acid in solution B
0.01mol/L；
2) according to elemental mole ratios nSn:nS=0.5:0.9 by SnCl2·2H2O is dissolved in above-mentioned solution B, until being completely dissolved
At solution C；
3) solution C homogeneous hydrothermal reaction kettle being put into seal, packing ratio is controlled 40%, is put into homogeneous hydro-thermal reaction instrument,
At 160 DEG C, the reaction time controls in 16h for reaction temperature control；
4) it waits for after reaction, taking out presoma, distinguishes centrifuge washing 3 times through deionized water and absolute ethyl alcohol, obtain black
Color presoma is dried in vacuo 12h at a temperature of 60 DEG C and obtains the spherical tin monoxide of particles self assemble/stannic oxide sodium ion electricity
Pond negative material.
Embodiment 2
1) thiocarbamide (TU) is dissolved in absolute ethyl alcohol, is configured to the solution A of a concentration of 0.26mol/L, made in magnetic agitation
Citric acid is added in above-mentioned solution A until be completely dissolved to form solution B with lower, makes a concentration of of citric acid in solution B
0.03mol/L；
2) according to elemental mole ratios nSn:nS=1.0:1.6 by SnCl2·2H2O is dissolved in above-mentioned solution B, until completely
It is dissolved into solution C；
3) C solution homogeneous hydrothermal reaction kettle being put into seal, packing ratio is controlled 50%, is put into homogeneous hydro-thermal reaction instrument,
At 180 DEG C, the reaction time controls in 18h for reaction temperature control；
4) it waits for after reaction, taking out presoma, distinguishes centrifuge washing 3 times through deionized water and absolute ethyl alcohol, obtain black
Color presoma is dried in vacuo 12h at a temperature of 60 DEG C and obtains the spherical tin monoxide of particles self assemble/stannic oxide sodium ion electricity
Pond negative material.
As can be seen from Figure 1 prepared sample corresponds to standard card PDF-07-0195SnO and standard card PDF- respectively
46-1088SnO2, it can also be seen that the crystallinity of the material and object are mutually preferable from XRD diagram；As can be seen from Figure 2 institute
It is nanoparticle to prepare tin monoxide/tin oxide, and diameter reaches 500nm~1um；From figure 3, it can be seen that in 100mAg-1
Under current density, discharge capacity 1433.5mAhg for the first time-1, 10 circles are recycled, capacity can reach 841.5mAhg-1, in big electricity
There is higher high rate performance, it is known that particle assembles spherical tin monoxide/tin oxide anode material of lithium-ion battery under current density
There is preferable capacity retention ratio under high current density.
Embodiment 3
1) thiocarbamide (TU) is dissolved in absolute ethyl alcohol, is configured to the solution A of a concentration of 0.50mol/L, made in magnetic agitation
Citric acid is added in solution A up to being completely dissolved to form solution B with lower, makes a concentration of 0.05mol/ of citric acid in solution B
L；
2) according to elemental mole ratios nSn:nS=2.0:3.0 by SnCl2·2H2O is dissolved in above-mentioned solution B, until completely
It is dissolved into solution C；
3) C solution homogeneous hydrothermal reaction kettle being put into seal, packing ratio is controlled 60%, is put into homogeneous hydro-thermal reaction instrument,
At 200 DEG C, the reaction time controls in 20h for reaction temperature control；
4) it waits for after reaction, taking out presoma, distinguishes centrifuge washing 3 times through deionized water and absolute ethyl alcohol, obtain black
Color presoma is dried in vacuo 12h at a temperature of 60 DEG C and obtains the spherical tin monoxide of particles self assemble/stannic oxide sodium ion electricity
Pond negative material.
Claims (7)
1. a kind of method that one-step method prepares the spherical tin monoxide of particles self assemble/stannic oxide anode material of lithium-ion battery,
It is characterized by comprising the following steps：
Step 1：Thiocarbamide is dissolved in absolute ethyl alcohol, solution A is configured to；Then solution A is added in citric acid under stirring
In until forming solution B after being completely dissolved；
Step 2：Under stirring according to elemental mole ratios nSn:nS=(0.5~2.0):(0.9~3.0) weighs SnCl2·
2H2O is dissolved in above-mentioned solution B and forms solution C；
Step 3：Solution C is subjected to homogeneous hydro-thermal reaction, obtains presoma after reaction；
Step 4：Presoma is distinguished into centrifuge washing several times through deionized water and absolute ethyl alcohol, then vacuum drying obtains
The spherical tin monoxide of particles self assemble/stannic oxide anode material of lithium-ion battery.
2. a kind of one-step method according to claim 1 prepares the spherical tin monoxide of particles self assemble/stannic oxide sodium ion
The method of cell negative electrode material, which is characterized in that a concentration of 0.13~0.50mol/L of solution A in step 1.
3. a kind of one-step method according to claim 1 prepares the spherical tin monoxide of particles self assemble/stannic oxide sodium ion
The method of cell negative electrode material, which is characterized in that in step 1 in solution B citric acid a concentration of 0.01~0.05mol/L.
4. a kind of one-step method according to claim 1 prepares the spherical tin monoxide of particles self assemble/stannic oxide sodium ion
The method of cell negative electrode material, which is characterized in that homogeneous hydro-thermal reaction is specially in step 3：Solution C is put into homogeneous hydro-thermal
Reaction kettle seals, and packing ratio is controlled 40%~60%, is put into homogeneous hydro-thermal reaction instrument and is reacted.
5. a kind of one-step method according to claim 4 prepares the spherical tin monoxide of particles self assemble/stannic oxide sodium ion
The method of cell negative electrode material, which is characterized in that the temperature of homogeneous hydro-thermal reaction is 160~200 DEG C, and the time is 16~20h.
6. a kind of one-step method according to claim 1 prepares the spherical tin monoxide of particles self assemble/stannic oxide sodium ion
The method of cell negative electrode material, which is characterized in that presoma is centrifuged respectively through deionized water and absolute ethyl alcohol in step 4 and is washed
It washs 3 times.
7. a kind of one-step method according to claim 1 prepares the spherical tin monoxide of particles self assemble/stannic oxide sodium ion
The method of cell negative electrode material, which is characterized in that vacuum drying temperature is 60 DEG C in step 4, time 12h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102602985A (en) * | 2012-04-11 | 2012-07-25 | 吉林大学 | Method for preparing nanometer stannous oxide and nanometer stannic oxide |
| CN103346299A (en) * | 2013-06-08 | 2013-10-09 | 上海大学 | In-situ etching method for preparing hollow tin-based oxide/carbon composite nano-material |
| CN105514404A (en) * | 2016-01-25 | 2016-04-20 | 陕西科技大学 | Nanoparticle assembled burr spherical SnO2 sodium-ion battery anode material and preparation method thereof |
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2018
- 2018-06-12 CN CN201810602613.0A patent/CN108807907B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102602985A (en) * | 2012-04-11 | 2012-07-25 | 吉林大学 | Method for preparing nanometer stannous oxide and nanometer stannic oxide |
| CN103346299A (en) * | 2013-06-08 | 2013-10-09 | 上海大学 | In-situ etching method for preparing hollow tin-based oxide/carbon composite nano-material |
| CN105514404A (en) * | 2016-01-25 | 2016-04-20 | 陕西科技大学 | Nanoparticle assembled burr spherical SnO2 sodium-ion battery anode material and preparation method thereof |
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