CN108695510A - A kind of preparation method of stannic selenide composite negative pole material - Google Patents
A kind of preparation method of stannic selenide composite negative pole material Download PDFInfo
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- CN108695510A CN108695510A CN201810740658.4A CN201810740658A CN108695510A CN 108695510 A CN108695510 A CN 108695510A CN 201810740658 A CN201810740658 A CN 201810740658A CN 108695510 A CN108695510 A CN 108695510A
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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
- H01M4/366—Composites as layered products
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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
- 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
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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
- H01M4/58—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
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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
- H01M4/58—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
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- 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
The invention discloses a kind of preparation methods of stannic selenide composite negative pole material, and preparation method of the present invention is simple, and experimental repeatability is high, the period is short, and the needs for being suitble to large-scale production to prepare have significant scientific meaning in terms of lithium ion battery applications;The stannic selenide that the method uses is covered with uniform through hole for nano-scale fiber shape on single fiber, and the volume expansion for effectively inhibiting stannic selenide is shunk;Humic acid is used for negative material carbon coating agent by the present invention, and negative material specific capacity is high, and cycle performance and high rate performance are excellent.
Description
Technical field
The present invention relates to battery material fields, and in particular to a kind of preparation method of stannic selenide composite negative pole material.
Background technology
The rapid development of modern industry, the mankind increasingly increase the demand of the energy.The world the utilized energy at present
85% comes from fossil feedstock (coal, oil, natural gas etc.), these raw materials be it is non-renewable, caused by environmental pollution
Constantly aggravating.Therefore, the development of green energy resource and its material, for realizing the 21st century strategy of sustainable development,
Alleviating energy crisis and mitigation pollution pressure all have very important significance.
It by lithium metal or lithium alloy is negative material, using the battery of non-aqueous electrolytic solution that lithium battery, which is a kind of,.Due to
The chemical characteristic of lithium metal is very active so that processing, preservation, the use of lithium metal, it is very high to environmental requirement, so, lithium
Battery is not applied for a long time, and with the development of technology, present lithium battery has become mainstream.Lithium battery can substantially divide
For two classes:Lithium metal battery and lithium ion battery.Lithium ion battery does not contain the lithium of metallic state, and can charge.Lithium
It is positive electrode that ion battery, which is usually using lithium alloy metals oxide, graphite is negative material.
However, the embedding lithium maximum capacity of theory of graphite is only 372mAh/g, and irreversible loss is big for the first time, multiplying power discharging
Can be poor, in addition, when lithium ion is embedded in, the partial solvent of electrolyte can also follow insertion, be easy to happen the variation of structure.Obviously
It cannot meet that automobile-used lithium ion battery is high-power, requirement of high power capacity.Therefore, in field of lithium, it is badly in need of negative material at present
Update.
Have studies have shown that the oxidation of nanometer transition metal has higher theoretical specific capacity, and capacity retention ratio is high.Especially
It is tin base cathode material, because tin base cathode not only has higher theoretical capacity, but also is easy to the member with the Vth main group
Element and the element of the VIth main group form the alloy cpd of two-phase.In recent years, for SnSb, Sn3P4,SnO2,SnS2The conjunction of equal tin
The report of gold compound is relatively more, but for SnSe2Report it is fewer.SnSe2For the layer structure of hexagonal phase, layer and layer
Between combination it is weaker, be conducive to the insertion and abjection of lithium ion, as negative material have larger development space.But
By SnSe2Negative material is applied in practice, and it still needs further improvement for chemical property.
Invention content
The present invention provides a kind of preparation method of stannic selenide composite negative pole material, preparation method letter of the present invention
Single, experimental repeatability is high, the period is short, the needs for being suitble to large-scale production to prepare, and has in terms of lithium ion battery applications notable
Scientific meaning;The stannic selenide that the method uses is covered with uniform through hole on single fiber, has for nano-scale fiber shape
Effect ground inhibits the volume expansion of stannic selenide to shrink;Humic acid is used for negative material carbon coating agent, negative material specific volume by the present invention
Amount is high, and cycle performance and high rate performance are excellent.
To achieve the goals above, the present invention provides a kind of preparation method of stannic selenide composite negative pole material, this method packet
Include following steps:
(1)Prepare porous selenizing tin material
Stannic chloride is taken to be add to deionized water, stirring to form solution one to being completely dissolved;Selenium powder is weighed, hydrazine hydrate is added to
In, stirring to form solution two to being completely dissolved;Then solution two is added dropwise to formation mixed solution three in solution one, and stirred
It mixes uniformly;Wherein, the molar ratio of tin ion and selenium atom is 1:(2-3);
Above-mentioned mixed liquor three is transferred in water heating kettle, water heating kettle is then placed in hydro-thermal reaction instrument in 220-230 DEG C of reaction, instead
It cools to room temperature after answering with the furnace, is then washed respectively with deionized water and absolute ethyl alcohol, centrifuges and obtain the powder of black, it will
Isolated powder dries to obtain SnSe2It is nanocrystalline.
By powdered potassium chloride and SnSe2It is nanocrystalline with mass ratio 10:(150-200)It is uniformly mixed, is then fed into spiral shell
The temperature of bar extruder, setting Screw Extrusion press is 340-350 DEG C, so that potassium chloride is ground by the rotational shear of screw rod, dispersion
Mill forms crystal grain and is dispersed in the SnSe of semi-molten state2It is nanocrystalline;
By to SnSe2Nanocrystalline to be sent into high temperature and pressure homogenizer while hot, setting temperature is 450-460 DEG C, and high pressure gas is nitrogen
Gas makes doped tin form injection stream and enters high voltage electrostatic spinning, obtain radial SnSe by homogenizer high temperature and pressure2Nanometer
Line;
The radial SnSe that will be obtained2Nano wire is cleaned with deionized water, removes remaining potassium chloride, and drying, refinement obtain porous
Stannic selenide;
(2)Commercial solid humic acid is added to the potassium hydroxide solution of 1-1.5mol/L, the matter of humic acid and potassium hydroxide solution
Amount is than being 1:(3-5), 60-65 DEG C of stirring 20-40min centrifuges, takes supernatant and be adjusted to pH=2-3, stand 12-14h, heavy
Starch is through the dry humic acid to get after refined;
(3)Humic acid after will be refined is added in the potassium hydroxide solution of 1-1.5mol/L, and heating, stirring are completely molten to solid
Solution;Above-mentioned porous stannic selenide is added, stirring, heating make moisture evaporating completely obtain solid, by solid abrasive to powdery;Exist again
950-1000 DEG C, calcine 2-4h in argon atmosphere, it is centrifugation, washing, dry to get stannic selenide composite negative pole material.
Preferably, a concentration of 14-15g/L of the humic acid in potassium hydroxide solution after refining, the humic acid after refining
Mass ratio with the porous stannic selenide is(6-7):(3.5-4).
The invention has the advantages that and remarkable result:
(1)Preparation method of the present invention is simple, and experimental repeatability is high, the period is short, the need for being suitble to large-scale production to prepare
It wants, there is significant scientific meaning in terms of lithium ion battery applications;
(2)The stannic selenide that the method uses is covered with uniform through hole, effectively for nano-scale fiber shape on single fiber
The volume expansion of stannic selenide is inhibited to shrink
(3)Humic acid is used for negative material carbon coating agent by the present invention, and negative material specific capacity is high, cycle performance and high rate performance
It is excellent.
Specific implementation mode
Embodiment one
Stannic chloride is taken to be add to deionized water, stirring to form solution one to being completely dissolved;Selenium powder is weighed, hydrazine hydrate is added to
In, stirring to form solution two to being completely dissolved;Then solution two is added dropwise to formation mixed solution three in solution one, and stirred
It mixes uniformly;Wherein, the molar ratio of tin ion and selenium atom is 1:2;Above-mentioned mixed liquor three is transferred in water heating kettle, then by water
Hot kettle is placed in hydro-thermal reaction instrument in 220 DEG C of reactions, cools to room temperature with the furnace after reaction, then uses deionized water and anhydrous second
Alcohol washs respectively, centrifuges and obtains the powder of black, dries isolated powder to obtain SnSe2It is nanocrystalline.It will be powdered
Potassium chloride and SnSe2It is nanocrystalline with mass ratio 10:150 are uniformly mixed, and are then fed into screw extruder, and Screw Extrusion press is arranged
Temperature be 340 DEG C, make potassium chloride grind to form crystal grain and be dispersed in semi-molten shape by the rotational shear of screw rod, dispersion
The SnSe of state2It is nanocrystalline.
By to SnSe2Nanocrystalline to be sent into high temperature and pressure homogenizer while hot, setting temperature is 450-460 DEG C, high pressure gas
So that doped tin is formed injection stream by homogenizer high temperature and pressure for nitrogen and enter high voltage electrostatic spinning, obtain radial SnSe2
Nano wire;The radial SnSe that will be obtained2Nano wire is cleaned with deionized water, removes remaining potassium chloride, and drying, refinement obtain
Porous stannic selenide.
Commercial solid humic acid is added to the potassium hydroxide solution of 1mol/L, the mass ratio of humic acid and potassium hydroxide solution
It is 1:3,60 DEG C of stirring 20min, centrifuge, take supernatant and be adjusted to pH=2, stand 12h, sediment is through dry to get refined
Humic acid afterwards.
Humic acid after refining is added in the potassium hydroxide solution of 1mol/L, and heating, stirring to solid are completely dissolved;Again
Above-mentioned porous stannic selenide is added, stirring, heating make moisture evaporating completely obtain solid, by solid abrasive to powdery;Again 950
DEG C, calcine 2h in argon atmosphere, it is centrifugation, washing, dry to get stannic selenide composite negative pole material.Wherein, the humic acid after refining
The mass ratio of a concentration of 14g/L in potassium hydroxide solution, humic acid and the porous stannic selenide after refining are 6:3.5.
Embodiment two
Stannic chloride is taken to be add to deionized water, stirring to form solution one to being completely dissolved;Selenium powder is weighed, hydrazine hydrate is added to
In, stirring to form solution two to being completely dissolved;Then solution two is added dropwise to formation mixed solution three in solution one, and stirred
It mixes uniformly;Wherein, the molar ratio of tin ion and selenium atom is 1:3;Above-mentioned mixed liquor three is transferred in water heating kettle, then by water
Hot kettle is placed in hydro-thermal reaction instrument in 230 DEG C of reactions, cools to room temperature with the furnace after reaction, then uses deionized water and anhydrous second
Alcohol washs respectively, centrifuges and obtains the powder of black, dries isolated powder to obtain SnSe2It is nanocrystalline.It will be powdered
Potassium chloride and SnSe2It is nanocrystalline with mass ratio 10:200 are uniformly mixed, and are then fed into screw extruder, and Screw Extrusion press is arranged
Temperature be 350 DEG C, make potassium chloride grind to form crystal grain and be dispersed in semi-molten shape by the rotational shear of screw rod, dispersion
The SnSe of state2It is nanocrystalline.
By to SnSe2Nanocrystalline to be sent into high temperature and pressure homogenizer while hot, setting temperature is 460 DEG C, and high pressure gas is nitrogen
Gas makes doped tin form injection stream and enters high voltage electrostatic spinning, obtain radial SnSe by homogenizer high temperature and pressure2Nanometer
Line;The radial SnSe that will be obtained2Nano wire is cleaned with deionized water, removes remaining potassium chloride, and drying, refinement obtain porous
Stannic selenide.
Commercial solid humic acid is added to the potassium hydroxide solution of 1.5mol/L, the quality of humic acid and potassium hydroxide solution
Than being 1:5,65 DEG C of stirring 40min, centrifuge, take supernatant and be adjusted to pH=3, stand 14h, sediment is through dry to get essence
Humic acid after system.
Humic acid after refining is added in the potassium hydroxide solution of 1.5mol/L, and heating, stirring to solid are completely dissolved;
Above-mentioned porous stannic selenide is added, stirring, heating make moisture evaporating completely obtain solid, by solid abrasive to powdery;Exist again
1000 DEG C, calcine 4h in argon atmosphere, it is centrifugation, washing, dry to get stannic selenide composite negative pole material.Wherein, the corruption after refining
The mass ratio of a concentration of 15g/L of the phytic acid in potassium hydroxide solution, humic acid and the porous stannic selenide after refining are 7:
4。
Using above-described embodiment one, two products therefrom materials as cathode of lithium battery is used for, with just extremely LiFePO 4 material
The test battery pack of composition carries out cyclical stability test, and discharge capacity is respectively 734mAh/g and 728mAh/g, cycle for the first time
Capacity is 692mAh/g and 687mAh/g after 200 times, has good cyclical stability.
Claims (2)
1. a kind of preparation method of stannic selenide composite negative pole material, this method comprises the following steps:
(1)Prepare porous selenizing tin material
Stannic chloride is taken to be add to deionized water, stirring to form solution one to being completely dissolved;Selenium powder is weighed, hydrazine hydrate is added to
In, stirring to form solution two to being completely dissolved;Then solution two is added dropwise to formation mixed solution three in solution one, and stirred
It mixes uniformly;Wherein, the molar ratio of tin ion and selenium atom is 1:(2-3);
Above-mentioned mixed liquor three is transferred in water heating kettle, water heating kettle is then placed in hydro-thermal reaction instrument in 220-230 DEG C of reaction, instead
It cools to room temperature after answering with the furnace, is then washed respectively with deionized water and absolute ethyl alcohol, centrifuges and obtain the powder of black, it will
Isolated powder dries to obtain SnSe2It is nanocrystalline;
By powdered potassium chloride and SnSe2It is nanocrystalline with mass ratio 10:(150-200)It is uniformly mixed, is then fed into screw extruding
The temperature of machine, setting Screw Extrusion press is 340-350 DEG C, makes potassium chloride grind to be formed by the rotational shear of screw rod, dispersion
Crystal grain and the SnSe for being dispersed in semi-molten state2It is nanocrystalline;
By to SnSe2Nanocrystalline to be sent into high temperature and pressure homogenizer while hot, setting temperature is 450-460 DEG C, and high pressure gas is nitrogen
Gas makes doped tin form injection stream and enters high voltage electrostatic spinning, obtain radial SnSe by homogenizer high temperature and pressure2Nanometer
Line;
The radial SnSe that will be obtained2Nano wire is cleaned with deionized water, removes remaining potassium chloride, and drying, refinement obtain porous
Stannic selenide;
(2)Commercial solid humic acid is added to the potassium hydroxide solution of 1-1.5mol/L, the matter of humic acid and potassium hydroxide solution
Amount is than being 1:(3-5), 60-65 DEG C of stirring 20-40min centrifuges, takes supernatant and be adjusted to pH=2-3, stand 12-14h, heavy
Starch is through the dry humic acid to get after refined;
(3)Humic acid after will be refined is added in the potassium hydroxide solution of 1-1.5mol/L, and heating, stirring are completely molten to solid
Solution;Above-mentioned porous stannic selenide is added, stirring, heating make moisture evaporating completely obtain solid, by solid abrasive to powdery;Exist again
950-1000 DEG C, calcine 2-4h in argon atmosphere, it is centrifugation, washing, dry to get stannic selenide composite negative pole material.
2. the method as described in claim 1, which is characterized in that the humic acid after refined is a concentration of in potassium hydroxide solution
14-15g/L, it is refined after the mass ratio of humic acid and the nano tin dioxide be(6-7):(3.5-4).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110190268A (en) * | 2019-06-24 | 2019-08-30 | 浙江大学 | A kind of SnSe2The preparation method of/CNTs composite lithium ion battery material |
| CN110504438A (en) * | 2019-08-31 | 2019-11-26 | 河南师范大学 | A kind of preparation method and applications of exotic atom doping carbon coating two-dimensional metallic selenides nanosheet composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784598A (en) * | 2016-12-19 | 2017-05-31 | 陕西科技大学 | A kind of used as negative electrode of Li-ion battery flake SnSe2Nanocrystalline preparation method |
| CN106935823A (en) * | 2017-03-20 | 2017-07-07 | 郑州大学 | A kind of lithium ion battery negative material Sn/C and preparation method thereof |
-
2018
- 2018-07-07 CN CN201810740658.4A patent/CN108695510A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784598A (en) * | 2016-12-19 | 2017-05-31 | 陕西科技大学 | A kind of used as negative electrode of Li-ion battery flake SnSe2Nanocrystalline preparation method |
| CN106935823A (en) * | 2017-03-20 | 2017-07-07 | 郑州大学 | A kind of lithium ion battery negative material Sn/C and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110190268A (en) * | 2019-06-24 | 2019-08-30 | 浙江大学 | A kind of SnSe2The preparation method of/CNTs composite lithium ion battery material |
| CN110504438A (en) * | 2019-08-31 | 2019-11-26 | 河南师范大学 | A kind of preparation method and applications of exotic atom doping carbon coating two-dimensional metallic selenides nanosheet composite material |
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