CN101174689A - Production method for tin-copper-cobalt ternary alloy cathode material of lithium ion battery - Google Patents
Production method for tin-copper-cobalt ternary alloy cathode material of lithium ion battery Download PDFInfo
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- CN101174689A CN101174689A CNA2007101764582A CN200710176458A CN101174689A CN 101174689 A CN101174689 A CN 101174689A CN A2007101764582 A CNA2007101764582 A CN A2007101764582A CN 200710176458 A CN200710176458 A CN 200710176458A CN 101174689 A CN101174689 A CN 101174689A
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- copper
- tin
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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 present invention discloses a preparation method of lithium-ion battery by Sn-Cu-Co alloy negative-pole materials, pertaining to the art of lithium-ion battery technology. The method is a carbon thermal reduction method to calculate the amount of Sn, Cu and Co oxides according to the Sn/(Cu+Co) atomic ratio of 3:1-2:3; wherein, the atomic ratio of Cu/Co is 5:1-1:5; the amount of carbon powder is calculated in terms of CO which is reduced from the oxygen in all oxides. After being evenly mixed and ground, the raw material is placed in a flowing protection atmosphere so as to rise to the required target temperature at a heating rate of 2-30 DEG C per minute and after a certain time of insulation, the temperature of the raw material declines to the room temperature with the cooling of furnace. The present invention has the advantages of low material cost, simple preparation process, less time consumption, high yield, good safety, great application value in material preparation and suitability for mass production. The Sn-Cu-Co alloy has the advantages that crystallization is higher; the inside is full of micron particles in a loose structure with a smaller surface, which are difficult to reunite in the electrode cycling process; the existence of the two non-active components Cu and Co greatly releases the volume changes in the electrode cycling process and is conducive to enhancing the stability of the electrode cycling.
Description
Technical field
The present invention relates to a kind of lithium ion battery negative material, particularly a kind of technology of preparing that adopts carbothermic method to prepare lithium ion battery tin copper-cobalt alloy negative material.
Background technology
Lithium ion battery is to satisfy one of high-energy battery of following social sustainable development requirement, but the capacity of its electrode material can not be greatly improved all the time, thereby has restricted the fast development of high-performance lithium ion battery.Most of business-like lithium ion battery all uses graphite type material as negative pole at present, the Theoretical Mass specific capacity of graphite-like material with carbon element is 372mAh/g, volume and capacity ratio is 800mAh/mL, through updating of people, now the actual specific capacity of material with carbon element is very near its theoretical specific capacity, thereby it is little further to improve the potentiality of carbon class negative material.In order to satisfy the demand of people to the height ratio capacity battery, must research and development cathode material for high capacity lithium ion battery of new generation.Tin can carry out reversible alloying and removal alloying reaction with lithium, has good doff lithium performance; When embedding lithium capacity reaches Li
22Sn
5The time, its specific discharge capacity can reach 994mAh/g, and volume and capacity ratio is about 7 times of material with carbon element; Because its removal lithium embedded current potential is a little more than material with carbon element, thereby security performance is good.So the Sn base alloy material is the lithium ion battery negative material of new generation that development potentiality is arranged very much.Hinder at present Sn base alloy material of cathode and realize that business-like subject matter is: embed and deviate from the process at lithium ion, the volume change of material is very big, easily causes the alloy anode structural deterioration, thereby influences the charge and discharge cycles stability of electrode.
People have proposed the kamash alloy electrode for this reason, use activity/activity or activity/non-active structure, make a kind of component or when the embedding lithium, another component or another the different or nonactive effect that can play the expansion of alleviation active component because of embedding lithium current potential mutually, thus reach the purpose that improves the material cycle performance.What extensively be studied at present is in the majority with the bianry alloy system, comprises Sn-Cu, Sn-Sb, Sn-Fe, Sn-Co and Sn-Ag etc.(Electrochemical Society such as Beattie, 2003,150 (7): A894-A898) prepared the Cu-Sn alloy with the pulse electrodeposition method, its preparation thinking is electro-deposition simple substance Sn on the Cu substrate, promote the interfacial reaction of Sn coating and Cu substrate then by heat treatment, thereby obtain the Cu-Sn alloy.Discover that the specific capacity of electrode reduces when the content of Cu in the alloy increases, and the change of capacity hold facility is good.(Acta PhySico-Chimica Sinica, 2006,22 (11): 1409-1412) adopt chemical reduction method to prepare the Co-Sn intermetallic compound of nano-scale, this method is to contain reducing agent NaBH to Xie Jian etc.
4Alkaline solution mix with the solution that contains metal ion and complexing agent, it is reacted at a certain temperature, with the product cyclic washing, vacuumize promptly gets required alloy.The Co that this method makes
3Sn
2Alloy shows the best stability that discharges and recharges owing to contain more non-active ingredient in the component.
The ternary alloy three-partalloy system comprises activity/activity/nonactive and active/nonactive/nonactive system, can expand by more effective inhibition electrode on this structural theory, improves the cyclical stability of electrode.(functional material such as Zheng Shufa; 2006,1 (37): 73-76) prepared the Sn-Sb-Mo ternary alloy three-partalloy with machine-alloying, this method is to put into ball mill behind the load weighted raw material blending; charge into argon gas and make protection gas, the ball milling certain hour can obtain the presoma product.The Sn-Sb-Mo alloy electrode of preparation has good removal lithium embedded performance through heat treatment after, discharge capacity 589mAh/g first, and 20 circulations still have the capacity of 451mAh/g afterwards.(J.Power Sources, 2007,167 (1): 171-177) use the same method and prepared Ni such as Zhang Jingjun
xCu
6-xSn
5Ternary alloy three-partalloy, test result show the increase along with Ni content, and the reversible capacity of this material descends, but cycle performance strengthens to some extent.Guo Hong etc. (CN20051013618.0) adopt carbothermic method to prepare the SnSbNi ternary alloy three-partalloy, and the high reversible capacity of this alloy reaches 379mAh/g.In this material, owing to exist Sn and two kinds of active components of Sb to participate in electrode reaction, make that the volumetric expansion phenomenon of electrode is more obvious in the removal lithium embedded process, so the stable circulation performance is not ideal enough, particularly more outstanding after repeatedly circulating.Preparations such as the preparation multiple purpose aeroplane tool alloying of ternary alloy three-partalloy system, liquid phase chemical reduction method, electrochemical deposition method at present, these method preparation cost of material height or complicated process of preparation or productive rate are low, are not easy to scale preparation.
Summary of the invention
The invention provides a kind of lithium ion battery preparation method with the Sn-Cu-Co alloy material of cathode, this method is to adopt carbothermic method, and as reducing agent, the oxide of reduction tin, copper and cobalt obtains the Sn-Cu-Co alloy of different atomic ratios with carbon dust.The material therefor cost is lower, and preparation technology's flow process is simple, and is consuming time few, and the productive rate height is pollution-free, has very big using value aspect material preparation, is fit to large-scale production.The tin copper-cobalt alloy that is synthesized is the higher micron particles of degree of crystallinity, and specific area is little, is difficult in the electrode cyclic process reuniting stable cycle performance.Simultaneously, because its little specific area, its surface impurity oxide is less, thereby it is lower to prepare the irreversible capacity first of material by this method.
The present invention adopts the concrete technology of the synthetic Sn-Cu-Co alloy material of cathode of high temperature solid-state reduction technique to be:
The oxide powder and the carbon dust of tin, copper, cobalt are carried out the weighing proportioning, and the atomic ratio that the addition of the oxide of tin, copper, cobalt is pressed Sn/ (Cu+Co) calculated in 3: 1～2: 3, and wherein the atomic ratio of Cu/Co is 5: 1～1: 5.The addition of carbon dust is by with the hydrogen reduction in all raw material oxides being CO calculating.
Oxide raw material is with SnO
2, CuO, Co
3O
4Be example, preparation Sn
xCu
yCo
zDuring the ternary alloy three-partalloy powder, carry out burdening calculation by chemical formula (1):
3xSnO
2+3yCuO+zCo
3O
4+(6x+3y+4z)C→3Sn
xCu
yCo
z+(6x+3y+4z)CO?↑ (1)
Wherein, x/ (y+z)=3: 1～2: 3, y/z=5: 1～1: 5.
Adopt mechanical dry method mixed or wet mixing that raw material is mixed; Mixture placed be connected with flowing nitrogen, argon gas or contain 2～10vol%H
2In the heating furnace of nitrogen, argon gas atmosphere, reach temperature required 800～1200 ℃, be incubated 1～6 hour, cool to room temperature then with the furnace, promptly obtain the tin-copper-cobalt ternary alloy powder with 2～30 ℃/minute heating rates.
The tin-copper-cobalt ternary alloy powder of above-mentioned gained can be used as the negative material of lithium ion battery.
Cu, Co are two kinds of toughness preferred metal elements, be introduced in the metal Sn, the huge change in volume that can buffers active component S n in the removal lithium embedded process, produces, improve the structural stability of electrode, thereby Sn-Cu-Co ternary alloy three-partalloy system is the rising lithium ion battery negative material of a class.
With existing method ratio, outstanding advantage of the present invention is:
1, the cost of material is low, and technological process is simple, consuming time few, the productive rate height.
2, synthesis condition is easy to control, no potential safety hazard.
3, in the tin copper-cobalt alloy with method preparation of the present invention, tin is active component, and copper and cobalt are non-active ingredient, so copper and cobalt can be used as frame material, alleviate the change in volume of tin in charge and discharge process to a great extent, thereby reach the purpose that improves the electrode material cyclical stability.
Description of drawings
Fig. 1 is X-ray powder diffraction (XRD) figure of the embodiment of the invention 2 gained tin copper-cobalt alloys, and in Fig. 1, abscissa is sweep limits (2-Theta), and ordinate is diffracted intensity (Intensity a.u.).
Fig. 2 is ESEM (SEM) figure of the embodiment of the invention 2 gained tin copper-cobalt alloys, and in Fig. 2, scale is 20 μ m.
Embodiment
Embodiment 1:
Accurately take by weighing 1gSnO, 0.1476g CuO, 0.1391gCoO and 0.1338g activated carbon are as initial feed (material molar ratio 4: 1: 1: 10, the atomic ratio that is equivalent to Sn/Cu/Co is 4: 1: 1), after grinding mixture evenly, place that the heating rate with 10 ℃/min is elevated to 1000 ℃ under the flowing nitrogen atmosphere, be incubated 3 hours, then outage, naturally cool to room temperature, promptly obtain the tin copper-cobalt alloy.
Embodiment 2:
Accurately take by weighing 1g SnO
2, 0.5279g CuO, 0.1065gCo
3O
4, and the 0.2604g activated carbon as initial feed (material molar ratio 15: 15: 1: 49, the atomic ratio that is equivalent to Sn/Cu/Co is 5: 5: 1), after grinding mixture evenly, place that the heating rate with 5 ℃/min is elevated to 900 ℃ under the mobile argon gas atmosphere, be incubated 2 hours, outage naturally cools to room temperature then, promptly obtains the tin copper-cobalt alloy.The XRD material phase analysis result of gained sample shows that synthetic product is Cu
6Sn
5, Sn and Co
3Sn
2Alloy complex does not have the existence of any oxide impurity phase.
Synthetic material is added the conductive agent acetylene black of 10wt%, and the binding agent PVDF of 10wt% makes slurry, evenly is applied on the Copper Foil, after the oven dry, blocks circular pole piece.With the lithium sheet is negative pole, the gained pole piece is anodal, used for electrolyte ethylene carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) (1: 1: 1) ternary electrolyte, barrier film is microporous polypropylene membrane Celgard2400, in being full of the glove box of argon gas, be assembled into simulated battery, carry out the constant current charge-discharge test.Charging and discharging currents is 100mA/g, and the charging/discharging voltage scope is controlled between the 0.02-1.5 V.Test result shows that the reversible capacity of this material is 250mAh/g, and 40 times circulation back capability retention is 93%.
Embodiment 3:
Accurately take by weighing 1g SnO
2, 0.2374g Cu
2O, 0.2486gCoO and 0.2192g carbon black are as initial feed (material molar ratio 4: 1: 2: 11, the atomic ratio that is equivalent to Sn/Cu/Co is 2: 1: 1), after grinding mixture evenly, place that the heating rate with 2 ℃/min is elevated to 800 ℃ under the mobile argon gas atmosphere, be incubated 2 hours, outage naturally cools to room temperature then, promptly obtains the tin copper-cobalt alloy.The XRD material phase analysis result of gained sample shows that synthetic product is Cu
6Sn
5And Co
3Sn
2Alloy complex does not have the existence of any oxide impurity phase.
Claims (3)
1. the preparation method of a tin-copper-cobalt ternary alloy cathode material of lithium ion battery is characterized in that, this preparation method may further comprise the steps:
A) oxide powder and the carbon dust with tin, copper, cobalt carries out the weighing proportioning, the atomic ratio that the addition of the oxide of tin, copper, cobalt is pressed Sn/ (Cu+Co) calculated in 3: 1～2: 3, wherein the atomic ratio of Cu/Co is 5: 1～1: 5, and the addition of carbon dust is by with the hydrogen reduction in all raw material oxides being CO calculating;
B) raw material is mixed after, place mobile protective atmosphere, reach temperature required 800～1200 ℃ with 2～30 ℃/minute heating rates, be incubated 1～6 hour;
C) cool to room temperature with the furnace, obtain end product Sn-Cu-Co alloy combination electrode material.
2. by the preparation method of the described tin-copper-cobalt ternary alloy cathode material of lithium ion battery of claim 1, it is characterized in that the particle diameter of the oxide raw material powder of described tin, copper and cobalt is micron order, submicron order or nanoscale.
3. by the preparation method of the described tin-copper-cobalt ternary alloy cathode material of lithium ion battery of claim 1, it is characterized in that the oxide of described tin is SnO
2Or SnO, the oxide of copper is CuO or Cu
2O, the oxide of cobalt are CoO or Co
3O
4
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| CNA2007101764582A CN101174689A (en) | 2007-10-29 | 2007-10-29 | Production method for tin-copper-cobalt ternary alloy cathode material of lithium ion battery |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105021024A (en) * | 2015-07-28 | 2015-11-04 | 深圳市贝特瑞新能源材料股份有限公司 | Microporous container used for deeply drying lithium ion battery powder materials and deep drying method |
| CN108493437A (en) * | 2018-03-19 | 2018-09-04 | 福建翔丰华新能源材料有限公司 | A method of preparing tin carbon lithium ion negative material |
| CN111668482A (en) * | 2019-03-08 | 2020-09-15 | 国家能源投资集团有限责任公司 | Electrode protection layer and preparation method thereof, electrode and lithium battery |
| CN112259726A (en) * | 2020-10-15 | 2021-01-22 | 湘潭大学 | Application of AlCuCo quasicrystal material |
| CN112349876A (en) * | 2020-10-27 | 2021-02-09 | 四川大学 | Hollow porous tin dioxide-cuprous oxide-copper and hollow porous tin dioxide-copper integrated lithium battery cathode and preparation method thereof |
| CN113130889A (en) * | 2020-01-16 | 2021-07-16 | 游萃蓉 | Negative electrode material for secondary battery, negative electrode, and secondary battery |
| WO2023126830A1 (en) * | 2021-12-27 | 2023-07-06 | Tata Steel Limited | A method of producing spherical copper powder and a product thereof |
| US11894556B2 (en) | 2020-01-16 | 2024-02-06 | National Tsing Hua University | Anode material for secondary battery, anode for secondary battery and secondary battery |
-
2007
- 2007-10-29 CN CNA2007101764582A patent/CN101174689A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105021024A (en) * | 2015-07-28 | 2015-11-04 | 深圳市贝特瑞新能源材料股份有限公司 | Microporous container used for deeply drying lithium ion battery powder materials and deep drying method |
| CN105021024B (en) * | 2015-07-28 | 2019-06-18 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of method of depth drying lithium ion battery powder material |
| CN108493437A (en) * | 2018-03-19 | 2018-09-04 | 福建翔丰华新能源材料有限公司 | A method of preparing tin carbon lithium ion negative material |
| CN108493437B (en) * | 2018-03-19 | 2020-11-24 | 福建翔丰华新能源材料有限公司 | Method for preparing tin-carbon lithium ion negative electrode material |
| CN111668482A (en) * | 2019-03-08 | 2020-09-15 | 国家能源投资集团有限责任公司 | Electrode protection layer and preparation method thereof, electrode and lithium battery |
| CN114725360A (en) * | 2020-01-16 | 2022-07-08 | 游萃蓉 | Negative electrode material for secondary battery, negative electrode, and secondary battery |
| CN113130889A (en) * | 2020-01-16 | 2021-07-16 | 游萃蓉 | Negative electrode material for secondary battery, negative electrode, and secondary battery |
| CN114725360B (en) * | 2020-01-16 | 2024-01-23 | 游萃蓉 | Negative electrode material for secondary battery, negative electrode, and secondary battery |
| US11894556B2 (en) | 2020-01-16 | 2024-02-06 | National Tsing Hua University | Anode material for secondary battery, anode for secondary battery and secondary battery |
| CN112259726B (en) * | 2020-10-15 | 2022-01-18 | 湘潭大学 | Application of AlCuCo quasicrystal material |
| CN112259726A (en) * | 2020-10-15 | 2021-01-22 | 湘潭大学 | Application of AlCuCo quasicrystal material |
| CN112349876A (en) * | 2020-10-27 | 2021-02-09 | 四川大学 | Hollow porous tin dioxide-cuprous oxide-copper and hollow porous tin dioxide-copper integrated lithium battery cathode and preparation method thereof |
| WO2023126830A1 (en) * | 2021-12-27 | 2023-07-06 | Tata Steel Limited | A method of producing spherical copper powder and a product thereof |
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