CN107528062A - A kind of preparation method of lithium battery tin base cathode material - Google Patents
A kind of preparation method of lithium battery tin base cathode material Download PDFInfo
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- CN107528062A CN107528062A CN201710209016.7A CN201710209016A CN107528062A CN 107528062 A CN107528062 A CN 107528062A CN 201710209016 A CN201710209016 A CN 201710209016A CN 107528062 A CN107528062 A CN 107528062A
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- China
- Prior art keywords
- mixed solution
- cathode material
- lithium battery
- temperature
- tin base
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- 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
-
- 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 method of lithium battery tin base cathode material, its step are as follows：(1) 0.8 g stannous oxalates, 0.23g titanium sulfates and 0.11g graphene oxides are mixed and added to 40ml deionized waters, stirred to being completely dissolved, obtain mixed solution；(2) 0.448g ammonium fluorides will be added in above-mentioned mixed solution, is encased in after stirring half an hour in ptfe autoclave, the hydro-thermal reaction 6h 72h at a temperature of for 120 DEG C 180 DEG C；(3) mixed solution after above-mentioned hydro-thermal reaction is removed into supernatant liquor, then filtered with deionized water and ethanol, washing, remove foreign ion；(4) 4h 18h are dried in vacuo at a temperature of the sample for eliminating foreign ion resulting in step (3) being placed on into 100 DEG C 120 DEG C, obtain dried powder；(5) vacuum heat 0h 8h, obtain lithium battery tin base cathode material at a temperature of above-mentioned dried powder being placed on into 180 DEG C 250 DEG C after heat treatment.This method preparation technology is simple, and preparation cost is relatively low, the stable cycle performance of the negative material, and electric transmission rate is high, and battery capacity can still reach 455.3mAh/g after the circle of circulation 200.
Description
Technical field
The present invention relates to a kind of preparation method of lithium battery tin base cathode material, belongs to lithium ion battery material technology neck
Domain.
Background technology
Lithium ion battery is high power capacity, high power battery.In order to meet ever-increasing application demand, lithium ion battery should
It is good that this is provided simultaneously with stable circulation performance, and reversible capacity is high, the chemical property such as fast charging and discharging.The requirement of these chemical properties
In cyclic process, migratory route of the lithium ion in negative material structure is as short as possible, lithium ion in its structure repeatedly
Volume Changes embedded and that abjection is caused are as small as possible, and the lithium storage content of negative material in itself is high as far as possible.But
The lithium cell cathode material of commercialization at present is mostly graphite, because graphite specific capacity is relatively low, potential safety hazard be present.In order to meet people
To the demand of battery performance, the chemical property for improving the negative material of lithium ion battery is the direction of development.
At present, tin base cathode material has turned into the focus of people's research, and tin-based material has higher theoretical specific capacity, often
The oxide for the tin seen includes SnO2(theoretical specific capacity 782mAh-1), SnO（Theoretical specific capacity 875mAhg-1), than the reason of graphite
It is much higher by capacity.But in charge and discharge process, tin-based material Volume Changes are larger, cause its cycle performance than relatively low.At present,
Many researchers put forth effort on the improvement of tin-based material, and the electric conductivity of tin-based material is improved by adulterating some compounds,
Middle volumetric expansion in cyclic process is reduced, so as to improve its electrochemistry cycle performance and high rate performance.Caixuan Xu et al. profit
SnO is adulterated with Zr2Negative material is prepared, effectively raises the electric conductivity of material, the volume reduced in discharge and recharge overshoot is swollen
It is swollen；Yang Tonghuan et al. utilizes carbon coating SnO2Negative material is prepared, effectively inhibits SnO2Reunion, improve battery capacity.
Although these researchs are so that the electric conductivity of battery is improved, it is suppressed that the volumetric expansion in cyclic process, these electricity
Pond prepares cost height, and cyclical stability is relatively weak, and with the increase of the circulation number of turns, the capacity of battery constantly reduces.
The content of the invention
For technical problem existing for prior art, the invention provides a kind of preparation side of lithium battery tin base cathode material
Method, this method preparation technology is simple, and preparation cost is relatively low, the stable cycle performance of the negative material, and electric transmission rate is high.
The present invention solves above-mentioned technical problem by the following technical programs：
The invention provides a kind of preparation method of lithium battery tin base cathode material, this method comprises the steps：
(1) the graphene oxide of 0.8g stannous oxalate, 0.23g titanium sulfate and 0.11g is mixed add to 40ml go from
Sub- water, stir to being completely dissolved, obtain mixed solution；
(2) 0.448g ammonium fluoride is added in the mixed solution that will be obtained in step (1), poly- four are encased in after stirring half an hour
In PVF reactor, the hydro-thermal reaction 6h-72h at a temperature of 120 DEG C -180 DEG C；
(3) mixed liquor after the hydro-thermal reaction that will be obtained in step (2) removes supernatant liquor, then with deionized water and ethanol mistake
Filter, washing, remove foreign ion；
(4) sample for eliminating foreign ion resulting in step (3) is placed at a temperature of 100 DEG C -120 DEG C and is dried in vacuo by
4h-18h, obtain dried powder；
(5) the h-8 h of vacuum heat 1 at a temperature of the dried powder obtained in step (4) is placed on 180 DEG C -250 DEG C by,
Lithium battery tin base cathode material is obtained after heat treatment.
The lithium battery tin base cathode material of the present invention has the advantage that：
The lithium ion battery negative material preparation method of the present invention is simple, and cost is relatively low；This method by stannous oxalate, titanium sulfate,
Graphene oxide, ammonium fluoride are compound to be prepared lithium battery tin base cathode material, and some spaces can be produced in the negative material, are had
The volumetric expansion of tin-based material during the buffer cycles of effect, the cycle performance of tin base cathode material is improved, reduce square resistance
It is small, improve electric transmission rate；Discharge and recharge is carried out by button cell is assembled into using electrode slice made from the negative material of the present invention
Performance test, after the circle of charge-discharge test circulation 200, battery capacity remains to reach 455.3mAh/g, and its square resistance is 10.64
Ω/□。
Embodiment
Raw material sources in following examples are as follows：
Stannous oxalate, ammonium fluoride, ethanol, titanium sulfate are commercially available prod.
Graphene oxide（GO）：Graphene oxide is prepared using Hummers methods（Sasha Stankovich, Richard
D. Piner, SonBinh T. Nguyen, Rodney S. Ruoff. Synthesis and exfoliation of
isocyanate-treated graphene oxide nanoplatelets. Carbon 2006, 44, 3342–
3347.）.
Below by embodiment, the present invention is described in detail.
Embodiment
A kind of preparation method of lithium battery tin base cathode material, this method comprise the steps：
(1) graphene oxide of 0.8g stannous oxalate, 0.23g titanium sulfate and 0.11g is mixed and adds 40ml deionizations by
Water, stir to being completely dissolved, obtain mixed solution；
(2) will add 0.448g ammonium fluoride in the obtained mixed solution of step (1), load polytetrafluoro after stirring half an hour
In the reactor of ethene, in 180 DEG C of hydro-thermal reaction 48h；
(3) mixed solution after the hydro-thermal reaction that will be obtained in step (2) removes supernatant liquor, then with deionized water and ethanol
Filtration washing, remove foreign ion；
(4) sample for eliminating foreign ion obtained in step (3) is placed at a temperature of 120 DEG C and is dried in vacuo 12h by, obtains
Dried powder；
(5) the dried powder obtained in step (4) is placed on vacuum heat 2.5h at 200 DEG C by, is obtained after heat treatment
Lithium battery tin base cathode material；
Square resistance after negative material tabletting is 10.64 Ω/, and being heat-treated influences little, compound on TiGFTO compounds
Chemical property is relatively stable.
For the charge and discharge effect of lithium battery tin base cathode material made from checking embodiment, the negative material that will be prepared
Electrode is made, preparing for electrode is as follows：0.01g Kynoar is put into 5ml beakers, instills few drops of dimethylformamides,
2h is stirred to whole dissolvings, obtains mixed solution；Lithium battery tin base cathode material obtained by 0.08g is mixed with 0.01g acetylene black
Grinding is uniform, adds in above-mentioned mixed solution, stirs 6h；Then it is applied on the copper foil cleaned by ethanol, at 120 DEG C
12h is dried in vacuo, is cut into slices after drying, is assembled into button cell progress charge-discharge performance test after electrode slice is made, it tests knot
Fruit is respectively：First circle capacity is 1130.9m Ah/g, and after the circle of circulation 50, capacity is reduced to 467.3mAh/g, after circulation 200 is enclosed, holds
Amount remains at 455.3mAh/g, and cycle performance is very stable；Square resistance after negative material tabletting is 10.64 Ω/, electronics
Transfer rate is higher.
Claims (1)
1. a kind of preparation method of lithium battery tin base cathode material, it is characterised in that this method comprises the steps：
(1) graphene oxide of 0.8 g stannous oxalate, 0.23g titanium sulfate and 0.11g is mixed to add to 40ml and gone
Ionized water, stir to being completely dissolved, obtain mixed solution；
(2) 0.448g ammonium fluoride is added in the mixed solution that will be obtained in step (1), poly- four are encased in after stirring half an hour
In PVF reactor, the hydro-thermal reaction 6h-72h at a temperature of for 120 DEG C -180 DEG C；
(3) mixed solution after the hydro-thermal reaction that will be obtained in step (2) removes supernatant liquor, then with deionized water and ethanol
Filtering, washing, remove foreign ion；
(4) sample for eliminating foreign ion resulting in step (3) is placed at a temperature of 100 DEG C -120 DEG C and be dried in vacuo
4h-18h, obtain dried powder；
(5) vacuum heat 10h-8h at a temperature of the dried powder obtained in step (4) being placed on into 180 DEG C -250 DEG C, heat
Lithium battery tin base cathode material is obtained after processing.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112271298A (en) * | 2020-10-22 | 2021-01-26 | 河北工业大学 | High-capacity nitrogen-doped carbon-coated SnOxPreparation method of quantum dot lithium ion battery cathode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569761A (en) * | 2010-12-08 | 2012-07-11 | 中国科学院金属研究所 | Titanium dioxide/graphene nanocomposite material and preparation method and application thereof |
| CN105529441A (en) * | 2015-09-17 | 2016-04-27 | 上海大学 | SnO<2>-TiO<2>@ graphene ternary composite nanomaterial and preparation method thereof |
| CN106099063A (en) * | 2016-07-28 | 2016-11-09 | 广东工业大学 | A kind of Hydrothermal Synthesis metal-oxide/graphene nanocomposite material and its preparation method and application |
| CN106450257A (en) * | 2016-11-16 | 2017-02-22 | 上海大学 | Doped stannic oxide and graphene composite material and preparing method thereof |
-
2017
- 2017-03-31 CN CN201710209016.7A patent/CN107528062A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569761A (en) * | 2010-12-08 | 2012-07-11 | 中国科学院金属研究所 | Titanium dioxide/graphene nanocomposite material and preparation method and application thereof |
| CN105529441A (en) * | 2015-09-17 | 2016-04-27 | 上海大学 | SnO<2>-TiO<2>@ graphene ternary composite nanomaterial and preparation method thereof |
| CN106099063A (en) * | 2016-07-28 | 2016-11-09 | 广东工业大学 | A kind of Hydrothermal Synthesis metal-oxide/graphene nanocomposite material and its preparation method and application |
| CN106450257A (en) * | 2016-11-16 | 2017-02-22 | 上海大学 | Doped stannic oxide and graphene composite material and preparing method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112271298A (en) * | 2020-10-22 | 2021-01-26 | 河北工业大学 | High-capacity nitrogen-doped carbon-coated SnOxPreparation method of quantum dot lithium ion battery cathode material |
| CN112271298B (en) * | 2020-10-22 | 2021-07-20 | 河北工业大学 | High-capacity nitrogen-doped carbon-coated SnOxPreparation method of quantum dot lithium ion battery cathode material |
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