CN101478038A - Process for preparing lithium ionic cell tin negative pole material by electrodepositing-hydrothermal process - Google Patents
Process for preparing lithium ionic cell tin negative pole material by electrodepositing-hydrothermal process Download PDFInfo
- Publication number
- CN101478038A CN101478038A CNA2008101641801A CN200810164180A CN101478038A CN 101478038 A CN101478038 A CN 101478038A CN A2008101641801 A CNA2008101641801 A CN A2008101641801A CN 200810164180 A CN200810164180 A CN 200810164180A CN 101478038 A CN101478038 A CN 101478038A
- Authority
- CN
- China
- Prior art keywords
- hydrothermal treatment
- treatment consists
- hydrothermal
- negative pole
- electro
- 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
Images
Classifications
-
- 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 method for preparing negative Sn electrode material of a Li-ion battery by electrodeposition and hydrothermal method. The method comprises the following steps: electrodepositing Sn on a Cu substrate; subjecting the Sn electrode to hydrothermal treatment with a hydrothermal treatment solution selected from a strong reducing agent containing hydrazine, sodium hypophosphite or sodium borohydride; washing the treated sample with deionized water; and drying at 80 to 120 DEG C to obtain the Sn electrode. The method has the advantages of simple operation, mild condition, easy control, and easy industrialization. The Sn electrode subjected to hydrothermal treatment has remarkably improved reversible capacity and exhibits excellent cycle performance. In addition, the reversible capacity keeps constant substantially after fifty cycles.
Description
Technical field
The present invention relates to the battery terminal preparation methods, especially relate to the method for a kind of electro-deposition-Hydrothermal Preparation lithium ionic cell tin negative pole material.
Background technology
Lithium ion battery has the voltage height, and specific capacity is big, discharging voltage balance, and advantages such as fail safe height have become at present one of the focus of the research and development in novel secondary chemical sources of electric energy field, and the improvement of its performance mainly depends on its anode and cathode active materials.The negative material of commercial applications mainly is a graphite type material at present, its theoretical specific capacity relatively low (about 320mAh/g), and along with the demand to high-capacity lithium ion cell, people begin to seek the high power capacity negative material that can replace material with carbon element.Sn can form Li with Li
22Sn
5Alloy, theoretical capacity can reach 993mAh/g, far above graphite material; To Li
+The operation current potential of/Li is 1.0～0.3V, can solve the deposition problems of lithium metal, does not have the common embedding of solvent in the charge and discharge process, to the solvent selectivity close friend; The processing characteristics and the electric conductivity of adding kamash alloy are good, do not have material with carbon element obvious to the sensitiveness of environment, and Sn base alloy is paid attention to and study lithium ion battery negative material the most widely at present most.
For tin negative pole material multiple preparation method is arranged, as chemical reduction method, electrodeposition process etc.Present more with these two kinds of methods, but because metal Sn is forming in the process of alloy with lithium, and change in volume is bigger, embedding repeatedly of lithium deviates to cause the mechanical stability of material to reduce gradually, thus efflorescence inefficacy gradually, cycle performance is poor.Therefore in order to overcome these unfavorable factors, many scholars have carried out a large amount of research, to improve the chemical property and the cycle performance of tin negative pole material.
Summary of the invention
The object of the present invention is to provide a kind of method of electro-deposition one Hydrothermal Preparation lithium ionic cell tin negative pole material.Electrodeposit metals tin on the copper matrix carries out hydrothermal treatment consists to tin electrode then, and hydrothermal treatment consists liquid is the solution that contains hydrazine or strong reductants such as inferior sodium phosphate or sodium borohydride.This method has improved the adhesion of metallic tin and copper matrix, and particle surface adheres to nonmetalloid, has improved the cycle performance of battery.
For the metallic tin negative pole, in charge and discharge process, because the embedding of taking off of lithium ion causes the efflorescence of tin particles and bursts apart, serious volumetric expansion takes place, the adhesion of tin and copper matrix weakens even comes off, and causes cycle performance poor.The present invention carries out hydrothermal treatment consists to tin electrode.Hydrothermal treatment consists liquid is the solution that contains hydrazine or strong reductants such as inferior sodium phosphate or sodium borohydride, can prevent that tin is oxidized, simultaneously at metallic tin surface recombination B or nonmetalloids such as P or N, has improved battery capacity; Form the Sn-Cu alloy between metallic tin and the matrix, improved adhesion, difficult drop-off in charge and discharge process, stable cycle performance.
The step of the technical solution used in the present invention is as follows:
(1) electrodeposit metals tin on the copper matrix;
(2) then tin electrode is carried out hydrothermal treatment consists; Hydrothermal treatment consists liquid is to contain hydrazine or contain inferior sodium phosphate or contain the solution of sodium borohydride strong reductant;
(3) with deionized water the sample after handling is washed,, obtain tin electrode 80-120 ℃ of drying.
The electro-deposition plating bath is alkalescence prescription-Na
2SnO
34H
2O 35～50g/L, NaOH 15～18g/L, NaAC 25～30g/L, current density is 0.2～0.6Adm
-2, temperature is 80～90 ℃, anode is a platinum electrode.
The temperature of described hydrothermal treatment consists is 100-300 ℃; The time of hydrothermal treatment consists is 5-48 hour.
Described hydrothermal treatment consists liquid is the solution that contains 0.0005～12.0ml/L hydrazine.
Described hydrothermal treatment consists liquid is the solution that contains 0.0001～10.0mol/L inferior sodium phosphate.
Described hydrothermal treatment consists liquid is the solution that contains 0.0001～10.0mol/L sodium borohydride.
The beneficial effect that the present invention has is:
The invention provides a kind of new method for preparing tin electrode: electro-deposition-hydro thermal method.Described hydrothermal treatment consists liquid is to contain hydrazine or contain inferior sodium phosphate or contain the solution of strong reductants such as sodium borohydride.This method is different from simple electrodeposition process and hydro thermal method, but has included the advantage of two kinds of methods, and the tin electrode of electrodeposition process preparation is compared the adhesion that can improve matrix and active material with coating method; Hydro thermal method has changed the pattern of electrode, forms the Cu-Sn alloy simultaneously, has also improved adhesion.With the metal tin electrode of electro-deposition-Hydrothermal Preparation, reversible capacity is improved significantly, and shows excellent cycle performance, and after 50 circulations, reversible capacity remains unchanged substantially.Operation is simple for this new method, mild condition, be easy to control, be easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 is the electromicroscopic photograph of electro-deposition Sn electrode before and after the hydrothermal treatment consists of the present invention.
Fig. 2 is the electrochemistry cycle performance of electro-deposition Sn electrode before and after the hydrothermal treatment consists of the present invention.
Embodiment
Electrodeposit metals tin on the copper matrix:
The electro-deposition plating bath is alkalescence prescription (the conventional prescription that uses)-Na
2SnO
34H
2O 35～50g/L, NaOH15～18g/L, NaAC 25～30g/L, current density is 0.2～0.6Adm
-2, temperature is 80～90 ℃, anode is a platinum electrode.
Embodiment 1:
Electrodeposit metals tin electrode in alkaline solution, then at 100 ℃ of hydrothermal treatment consists 48h, the concentration of hydrazine solution is 0.0005ml/L, with deionized water the sample after handling is washed, 100 ℃ of following vacuumizes, the sample that present embodiment obtains, after 50 circulations, capacity still remains on 500mAh/g.
Embodiment 2:
Electrodeposit metals tin electrode in alkaline solution, then at 150 ℃ of hydrothermal treatment consists 24h, the concentration of hydrazine solution is 0.1ml/L, with deionized water the sample after handling is washed, at 80 ℃ of following vacuumizes, the sample that present embodiment obtains, after 50 circulations, capacity still remains on 550mAh/g.
Embodiment 3:
Electrodeposit metals tin electrode in alkaline solution, then at 300 ℃ of hydrothermal treatment consists 5h, the concentration of hydrazine solution is 12.0ml/L, with deionized water the sample after handling is washed, at 100 ℃ of following vacuumizes, the sample that present embodiment obtains, after 50 circulations, capacity still remains on 520mAh/g.
Embodiment 4:
Electrodeposit metals tin electrode in alkaline solution, then at 200 ℃ of hydrothermal treatment consists 5h, the concentration of ortho phosphorous acid sodium solution is 0.0001mol/L, with deionized water the sample after handling is washed, 80 ℃ of following vacuumizes, the sample that present embodiment obtains, after 50 circulations, capacity still remains on 483mAh/g.
Embodiment 5:
Electrodeposit metals tin electrode in alkaline solution, then at 300 ℃ of hydrothermal treatment consists 10h, the concentration of ortho phosphorous acid sodium solution is 10.0mol/L, with deionized water the sample after handling is washed, 90 ℃ of following vacuumizes, the sample that present embodiment obtains, after 50 circulations, capacity still remains on about 512mAh/g.
Embodiment 6:
Electrodeposit metals tin electrode in alkaline solution, then at 100 ℃ of hydrothermal treatment consists 48h, the concentration of ortho phosphorous acid sodium solution is 0.15mol/L, with deionized water the sample after handling is washed, 100 ℃ of following vacuumizes, the sample that present embodiment obtains, after 50 circulations, capacity still remains on about 560mAh/g.
Embodiment 7:
Electrodeposit metals tin electrode in alkaline solution, at 180 ℃ of hydrothermal treatment consists 48h, the concentration of sodium borohydride solution is 0.0001mol/L, with deionized water the sample after handling is washed, 80 ℃ of following vacuumizes, the sample that present embodiment obtains, after 50 circulations, capacity still remains on 450mAh/g.
Embodiment 8:
Electrodeposit metals tin electrode in alkaline solution, at 250 ℃ of hydrothermal treatment consists 5h, the concentration of sodium borohydride solution is 10.0mol/L, with deionized water the sample after handling is washed, at 80 ℃ of following vacuumizes, the sample that present embodiment obtains, after 50 circulations, capacity still remains on 475mAh/g.
Embodiment 9:
Electrodeposit metals tin electrode in alkaline solution, at 100 ℃ of hydrothermal treatment consists 20h, the concentration of sodium borohydride solution is 5.0mol/L, with deionized water the sample after handling is washed, at 90 ℃ of following vacuumizes, the sample that present embodiment obtains, after 50 circulations, capacity still remains on 510mAh/g.
Embodiment 10:
Electrodeposit metals tin electrode in alkaline solution, then at 150 ℃ of hydrothermal treatment consists 30h, the concentration of sodium borohydride solution is 0.015mol/L, with deionized water the sample after handling is washed, 100 ℃ of following vacuumizes, the sample that present embodiment obtains, after 50 circulations, capacity still remains on about 600mAh/g.Cycle performance as shown in Figure 2.
As shown in Figure 1, the metallic tin negative material of the present invention's preparation is the tin electrode hydrothermal treatment consists gained to electro-deposition, and hydrothermal treatment consists liquid is the solution that contains hydrazine or strong reductants such as inferior sodium phosphate or sodium borohydride.Tin electrode before handling is tiny and uniform particle, smooth surface, and variation has taken place in electrode pattern and structure after handling, and occurs some micropore/passages between the particle, and rough surface, and the material of one deck black is arranged, and the EDAX proof has been adhered to nonmetalloid.These micropores and coarse surface help the embedding of taking off of lithium ion, suppress volumetric expansion, increase the Drawability of material, and change in volume is reduced greatly, help improving the cycle life of electrode, obtain high power capacity.
Claims (6)
1, the method for a kind of electro-deposition-Hydrothermal Preparation lithium ionic cell tin negative pole material is characterized in that the step of this method is as follows:
(1) electrodeposit metals tin on the copper matrix;
(2) then tin electrode is carried out hydrothermal treatment consists; Hydrothermal treatment consists liquid is to contain hydrazine or contain inferior sodium phosphate or contain the solution of sodium borohydride strong reductant;
(3) with deionized water the sample after handling is washed,, obtain tin electrode 80-120 ℃ of drying.
2, the method for a kind of electro-deposition according to claim 1-Hydrothermal Preparation lithium ionic cell tin negative pole material is characterized in that: the electro-deposition plating bath is alkalescence prescription-Na
2SnO
34H
2O35～50g/L, NaOH15～18g/L, NaAC25～30g/L, current density is 0.2～0.6Adm
-2, temperature is 80～90 ℃, anode is a platinum electrode.
3, the method for a kind of electro-deposition according to claim 1-Hydrothermal Preparation lithium ionic cell tin negative pole material, it is characterized in that: the temperature of described hydrothermal treatment consists is 100-300 ℃; The time of hydrothermal treatment consists is 5-48 hour.
4, the method for a kind of electro-deposition according to claim 1-Hydrothermal Preparation lithium ionic cell tin negative pole material, it is characterized in that: described hydrothermal treatment consists liquid is the solution that contains 0.0005～12.0ml/L hydrazine.
5, the method for a kind of electro-deposition according to claim 1-Hydrothermal Preparation lithium ionic cell tin negative pole material, it is characterized in that: described hydrothermal treatment consists liquid is the solution that contains 0.0001～10.0mol/L inferior sodium phosphate.
6, the method for a kind of electro-deposition according to claim 1-Hydrothermal Preparation lithium ionic cell tin negative pole material, it is characterized in that: described hydrothermal treatment consists liquid is the solution that contains 0.0001～10.0mol/L sodium borohydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101641801A CN101478038B (en) | 2008-12-29 | 2008-12-29 | Process for preparing lithium ionic cell tin negative pole material by electrodepositing-hydrothermal process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101641801A CN101478038B (en) | 2008-12-29 | 2008-12-29 | Process for preparing lithium ionic cell tin negative pole material by electrodepositing-hydrothermal process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101478038A true CN101478038A (en) | 2009-07-08 |
| CN101478038B CN101478038B (en) | 2010-12-01 |
Family
ID=40838693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101641801A Expired - Fee Related CN101478038B (en) | 2008-12-29 | 2008-12-29 | Process for preparing lithium ionic cell tin negative pole material by electrodepositing-hydrothermal process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101478038B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104868111A (en) * | 2015-03-27 | 2015-08-26 | 陕西科技大学 | Preparation method of Ce doped Li4Ti5O12 lithium ion battery cathode material |
| CN106868538A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of Carbon dioxide electrochemical reduction electrode, preparation method and applications |
| CN111276672A (en) * | 2020-02-14 | 2020-06-12 | 苏州大学 | Preparation and application of electrode containing tin array structure |
| CN111996548A (en) * | 2020-05-19 | 2020-11-27 | 大连大学 | Preparation and application of ZnSn electrode for electrochemical reduction of carbon dioxide |
-
2008
- 2008-12-29 CN CN2008101641801A patent/CN101478038B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104868111A (en) * | 2015-03-27 | 2015-08-26 | 陕西科技大学 | Preparation method of Ce doped Li4Ti5O12 lithium ion battery cathode material |
| CN106868538A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of Carbon dioxide electrochemical reduction electrode, preparation method and applications |
| CN106868538B (en) * | 2015-12-13 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of Carbon dioxide electrochemical reduction electrode, preparation method and applications |
| CN111276672A (en) * | 2020-02-14 | 2020-06-12 | 苏州大学 | Preparation and application of electrode containing tin array structure |
| CN111996548A (en) * | 2020-05-19 | 2020-11-27 | 大连大学 | Preparation and application of ZnSn electrode for electrochemical reduction of carbon dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101478038B (en) | 2010-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101144176B (en) | Method for reducing metal and alloy hydroxide gel by hydrogen separated from electrochemistry cathode | |
| CN103227057B (en) | A kind of method preparing manganese dioxide electrode of super capacitor | |
| CN102201590A (en) | Acidic zinc single liquid flow energy storage battery | |
| CN102903924A (en) | Battery | |
| CN109301186B (en) | Coated porous ternary cathode material and preparation method thereof | |
| CN113270577B (en) | Aqueous zinc ion battery and positive electrode material | |
| CN101478038B (en) | Process for preparing lithium ionic cell tin negative pole material by electrodepositing-hydrothermal process | |
| CN103094583A (en) | Battery and treatment method of battery current collector | |
| CN112909229A (en) | Silver coating method of three-dimensional lithium-philic metal foam framework and preparation method of application of silver coating method in lithium metal negative electrode | |
| CN110137430A (en) | The Co of three-dimensional porous array structure3O4/ rGO/Ni foam combination electrode material and preparation method thereof | |
| CN103094524A (en) | Tin alloy membrane electrode and application thereof | |
| CN109148899A (en) | A kind of preparation method of aluminium-air cell cathode | |
| CN103137956B (en) | The lithium ion battery negative material nickeltin powder preparation method of a kind of porous, chondritic | |
| CN112921369B (en) | Lithium metal negative current collector surface thermal oxidation regulation and control method for prolonging cycle life | |
| US3753779A (en) | Method of making zinc electrodes | |
| CN106601993A (en) | Lithium ion battery negative electrode plate and preparation method therefor | |
| CN108642533B (en) | Sn-Cu electroplating solution, tin-based alloy electrode for lithium ion battery, preparation method of tin-based alloy electrode and lithium ion battery | |
| CN107785607B (en) | Sodium ion battery with novel structure and preparation method thereof | |
| CN201562714U (en) | Button battery with electroplated layer at negative current collection body | |
| CN111009653B (en) | Preparation method of zinc cathode material of zinc-nickel secondary battery | |
| CN114481101B (en) | Metal material obtained by method for regulating and controlling crystal face orientation of metal coating and application | |
| CN117542948B (en) | Water-based zinc ion battery negative electrode material, preparation method and zinc ion battery | |
| CN116130795A (en) | Electrolyte additive and application thereof in water-based zinc ion battery | |
| CN114824151A (en) | Metal zinc cathode protected by chemical passivation layer and preparation method and application thereof | |
| CN117317122A (en) | Zinc anode material with high specific surface area and zinc affinity, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101201 Termination date: 20131229 |