CN100565978C - The tin-cobalt alloy negative electrode material of lithium ion battery and preparation method - Google Patents
The tin-cobalt alloy negative electrode material of lithium ion battery and preparation method Download PDFInfo
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- CN100565978C CN100565978C CNB2007100576088A CN200710057608A CN100565978C CN 100565978 C CN100565978 C CN 100565978C CN B2007100576088 A CNB2007100576088 A CN B2007100576088A CN 200710057608 A CN200710057608 A CN 200710057608A CN 100565978 C CN100565978 C CN 100565978C
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- cobalt alloy
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Abstract
The present invention relates to the tin-cobalt alloy negative electrode material and the preparation method of lithium ion battery.The tin-cobalt alloy negative electrode material of ion battery wherein contains Sn, Co at least
3Sn
2, CuSn or CoSn
3Two kinds of materials, there are luxuriant shape and spherical two kinds of shapes in the surface, size is 5～50 μ m.The preparation method of the tin-cobalt alloy negative electrode material of lithium ion battery of the present invention, 1) at first on the copper matrix, adheres to one deck tin; 2) preparation plating bath: pink salt 10～50g/L, cobalt salt 5～20g/L, K
4P
2O
73H
2O100～400g/L, citric acid 10～30g/L, glycine 10～30g/L, methionine 2～10g/L; 3) pass through electro-deposition method: 15～35 ℃ of control temperature, pH=8～9, current density is 5～20mA/cm
2, be 0.5～2.5h conduction time, obtains the tin-cobalt alloy material.Serious reunion and surface oxidation be difficult for to take place in the tin-cobalt alloy degree of crystallinity height that the present invention prepares, and have reduced the irreversible capacity of negative material, and reversible capacity is up to 545mAh/g, circulate still to remain on more than the 400mAh/g after 10 times.
Description
Technical field
The present invention relates to the lithium ion battery negative material technical field.The tin-cobalt alloy negative electrode material and the preparation method that particularly relate to lithium ion battery.
Background technology
Lithium ion battery is the green high-capacity rechargeable battery of latest generation, be on the basis of lithium secondary battery research, in the novel power supply system that early 1990s develops rapidly, have that voltage height, energy density are big, outstanding advantages such as good cycle, self discharge are little, memory-less effect.Obtained develop rapidly over nearly 10 years, and occupied leading position in mobile electronic terminal apparatus field such as notebook computer, mobile phone, video camera, weaponrys with its remarkable high performance price ratio advantage, be considered to 21 century to national economy and the significant new high-tech product of people's lives.
Present business-like lithium ion battery negative material adopts carbon class material mostly, though the chemical property excellence of this material, lithium storage content is lower.Its actual specific capacity is at present very near its theoretical specific capacity, further the potentiality of its specific capacity of exploitation are very little, thereby are difficult to adapt to the widespread demand of the development of the miniaturization development of present various portable electric appts and electric automobile to the large-capacity high-power chemical power source.Therefore, research and develop new type lithium ion battery negative material and become current research focus with height ratio capacity.
Tin can carry out reversible alloying and removal alloying reaction with lithium, has good doff lithium performance; Form Li
4.4During the Sn alloy, its Theoretical Mass specific capacity is 994mAh/g, and volume and capacity ratio more can be up to 7200mAh/cm
3, thereby be a kind of very promising negative material, receive the concern of various countries.But metallic tin is in doff lithium process repeatedly, because tin atom comparatively softness and fusing point is lower, easily be gathered into cluster, in case form in the cluster material and two-phase section will occur, cause that volume does not match in the cyclic process, can cause material of main part fragmentation, efflorescence, thereby make the efficiency for charge-discharge of electrode reduce, cycle performance is very poor, thereby can not be merely with the negative material of metallic tin as lithium-ions battery.In order to solve the expansion issues of material of main part, people have proposed to prepare the method for tin-oxide and kamash alloy electrode.Though tin-oxide is because the Li that forms during first embedding lithium
2O can expand by the good restraining electrode as the buffering matrix, improves electrode performance, but just has the excessive problem of irreversible capacity that circulates first thus; And kamash alloy adopts activity/nonactive or active/active structure, owing to be subjected to the cushioning effect of other elements, can effectively suppress electrode and expand during doff lithium, has improved the cycle life of electrode.Thereby kamash alloy becomes the research focus of current negative electrode of lithium secondary batteries.
Summary of the invention
The objective of the invention is to adopt the method for electro-deposition, prepare the tin-cobalt alloy negative electrode material of different proportion, be used to improve the chemical property of tin-cobalt alloy negative electrode material, mainly is raising capacity and cycle performance.
Technical scheme of the present invention is as follows:
The tin-cobalt alloy negative electrode material of a kind of lithium ion battery of the present invention wherein contains Sn, Co at least
3Sn
2, CuSn or CoSn
3Two kinds of materials, there are luxuriant shape and spherical two kinds of shapes in the surface, size is 5～50 μ m.
The tin-cobalt alloy negative electrode material of lithium ion battery of the present invention, component and weight percent content are as follows:
Sn： 70～93
Co： 7～30。
The preparation method of the tin-cobalt alloy negative electrode material of lithium ion battery of the present invention, its step is as follows:
1) at first on the copper matrix, adheres to one deck tin;
2) preparation plating bath: pink salt 10～50g/L, cobalt salt 5～20g/L, K
4P
2O
73H
2O100～400g/L, citric acid 10～30g/L, glycine 10～30g/L, methionine 2～10g/L;
3) pass through electro-deposition method: 15～35 ℃ of control temperature, Ph=8～9, current density is 5～20mA/cm
2, energising
Time is 0.5～2.5h, obtains the tin-cobalt alloy material.
Described pink salt comprises SnCl
22H
2O, SnSO
4, described cobalt salt comprises CoCl
2, CoSO
4
The invention has the advantages that technical process is simple, consuming time less.The tin-cobalt alloy degree of crystallinity height of preparing be 3～50 microns polycrystalline particle, thereby specific area is lower, is difficult for serious reunion and surface oxidation take place, and has reduced the irreversible capacity of negative material.The tin-cobalt alloy lithium ion battery negative material specific capacity height of preparing, stable cycle performance, reversible capacity is up to 545mAh/g, circulates still to remain on more than the 400mAh/g after 10 times.
Description of drawings
Fig. 1: be the XRD figure of tin-cobalt alloy among the embodiment 1.
Fig. 2: be the SEM figure of tin-cobalt alloy among the embodiment 1.
Fig. 3: be the specific capacity-cycle-index curve of tin-cobalt alloy negative electrode material among the embodiment 1.
Fig. 4: be the XRD figure of tin-cobalt alloy among the embodiment 2.
Fig. 5: be the SEM figure of tin-cobalt alloy among the embodiment 2.
Fig. 6: be the specific capacity-cycle-index curve of tin-cobalt alloy negative electrode material among the embodiment 2.
Fig. 7: be the XRD figure of tin-cobalt alloy among the embodiment 3.
Fig. 8: be the SEM figure of tin-cobalt alloy among the embodiment 3.
Fig. 9: be the specific capacity-cycle-index curve of tin-cobalt alloy negative electrode material among the embodiment 3.
Embodiment
At first before the electrotinning cobalt alloy, on Copper Foil, adhere to one deck tin earlier.Then, deposit tin cobalt alloy again, cobalt has good ductility, the volumetric expansion that produces in the time of suppressing to form lithium-tin alloy in the charge and discharge process and the efflorescence of the rear electrode that repeatedly circulates.Electroplating technical conditions is as follows.
Plating bath is formed: 50g/L SnCl
22H
2O, 15g/L CoCl
2, 200g/L K
4P
2O
73H
2O, 10g/L citric acid 1,10g/L glycine, 3g/L methionine, Ph=8～9.
Current density: 15mA/cm
2
Sedimentation time: 1h.
Post-processed: the electro-deposition sheet after washed with de-ionized water, with hair-dryer cold wind blow in, obtain tin-cobalt alloy negative electrode material, the percentage by weight of Co is 7.56%.
Fig. 1 is the XRD figure of tin-cobalt alloy among the embodiment 1, can determine to exist in the coating CoSn
3, Cu
41Sn
11Alloy structure and Sn and Co simple substance.
Fig. 2 is the SEM figure of tin-cobalt alloy among the embodiment 1, and visible coating surface is coarse, has spherical particle, and size is evenly distributed about 40 microns.
Fig. 3 is the specific capacity-cycle-index curve of tin-cobalt alloy of the present invention, and its initial charge capacity is 316.8mAh/g, and discharge capacity is 545.3mAh/g first, and the capacity after 10 circulations is more than 400mAh/g.
At first before the electrotinning cobalt alloy, on Copper Foil, adhere to one deck tin earlier.Then, deposit tin cobalt alloy again, cobalt has good ductility, the volumetric expansion that produces in the time of suppressing to form lithium-tin alloy in the charge and discharge process and the efflorescence of the rear electrode that repeatedly circulates.Electroplating technical conditions is as follows.
Plating bath is formed: 30g/L SnCl
22H
2O, 15g/L CoCl
2, 200g/L K
4P
2O
73H
2O, 10g/L citric acid 1,10g/L glycine, 3g/L methionine, Ph=8～9.
Current density: 5mA/cm
2
Sedimentation time: 2.5h.
Post-processed: the electro-deposition sheet dries up with hair-dryer cold wind after washed with de-ionized water, obtains tin-cobalt alloy negative electrode material, and the percentage by weight of Co is 13.50%.
Fig. 4 is the XRD figure of tin-cobalt alloy among the embodiment 2, can determine to exist in the coating CuSn and CoSn
3Alloy structure.
Fig. 5 is the SEM figure of tin-cobalt alloy among the embodiment 2, and visible coating surface is luxuriant shape structure, and size is about 5 microns.
Fig. 6 is the specific capacity-cycle-index curve of tin-cobalt alloy negative electrode material among the embodiment 2, and its initial charge capacity is 100mAh/g, and discharge capacity is 159.5mAh/g first, and the capacity after 10 circulations is more than 170mAh/g.
At first before the electrotinning cobalt alloy, on Copper Foil, adhere to one deck tin earlier.Then, deposit tin cobalt alloy again, cobalt has good ductility, the volumetric expansion that produces in the time of suppressing to form lithium-tin alloy in the charge and discharge process and the efflorescence of the rear electrode that repeatedly circulates.Electroplating technical conditions is as follows.
Plating bath is formed: 10g/L SnCl
22H
2O, 15g/L CoCl
2, 200g/L K
4P
2O
73H
2O, 10g/L citric acid 1,10g/L glycine, 3g/L methionine, Ph=8～9.
Current density: 20mA/cm
2
Sedimentation time: 0.5h.
Post-processed: the electro-deposition sheet dries up with hair-dryer cold wind after washed with de-ionized water, obtains tin-cobalt alloy negative electrode material, and the percentage by weight of Co is 22.63%.
Fig. 7 is the XRD figure of tin-cobalt alloy among the embodiment 3, can determine to exist in the coating CuSn alloy structure Sn simple substance.
Fig. 8 is the SEM figure of tin-cobalt alloy among the embodiment 3, and visible coating surface is luxuriant shape structure, and size is about 4 microns.
Fig. 9 is the specific capacity-cycle-index curve of tin-cobalt alloy negative electrode material among the embodiment 3, and its initial charge capacity is 347mAh/g, and discharge capacity is 1642.7mAh/g first, and the capacity after 10 circulations is more than 125mAh/g.
The tin-cobalt alloy negative electrode material and the preparation method of the lithium ion battery that the present invention discloses and discloses.Can be by using for reference this paper disclosure.Although material of the present invention and method are described by preferred embodiment, but those skilled in the art obviously can change method as herein described in not breaking away from content of the present invention, spirit and scope, more particularly, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (4)
1. the tin-cobalt alloy negative electrode material of a lithium ion battery is characterized in that: contain Co
3Sn
2, CuSn or CoSn
3Two kinds of materials, there are luxuriant shape and spherical two kinds of shapes in the tin-cobalt alloy surface, luxuriant shape and spherical diameter are 5～50 μ m.
2. the tin-cobalt alloy negative electrode material of lithium ion battery as claimed in claim 1 is characterized in that described material component and weight percent content are as follows:
Sn：70～93
Co：7～30。
3. the preparation method of the tin-cobalt alloy negative electrode material of claim 1 or 2 described lithium ion batteries is characterized in that step is as follows:
1) at first on the copper matrix, adheres to one deck tin;
2) preparation plating bath: pink salt 10～50g/L, cobalt salt 5～20g/L, K
4P
2O
73H
2O100～400g/L, citric acid 10～30g/L, glycine 10～30g/L, methionine 2～10g/L;
3) pass through electro-deposition method: 15～35 ℃ of control temperature, Ph=8～9, current density is 5～20mA/cm
2, be 0.5～2.5h conduction time, obtains the tin-cobalt alloy material.
4. the preparation method of the tin-cobalt alloy negative electrode material of lithium ion battery as claimed in claim 3 is characterized in that described pink salt is selected from SnCl
22H
2O or SnSO
4Wherein a kind of; Cobalt salt is selected from CoCl
2Or CoSO
4Wherein a kind of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100576088A CN100565978C (en) | 2007-06-13 | 2007-06-13 | The tin-cobalt alloy negative electrode material of lithium ion battery and preparation method |
Applications Claiming Priority (1)
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|---|---|---|---|
| CNB2007100576088A CN100565978C (en) | 2007-06-13 | 2007-06-13 | The tin-cobalt alloy negative electrode material of lithium ion battery and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101071851A CN101071851A (en) | 2007-11-14 |
| CN100565978C true CN100565978C (en) | 2009-12-02 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2015002323A (en) * | 2012-08-27 | 2015-06-05 | Nippon Steel & Sumitomo Metal Corp | Negative electrode active substance material. |
| CN103137956B (en) * | 2013-03-15 | 2015-08-12 | 中国计量学院 | The lithium ion battery negative material nickeltin powder preparation method of a kind of porous, chondritic |
| CN107845804B (en) * | 2016-09-19 | 2021-03-02 | 天津大学 | Silicon-tin composite negative electrode material of lithium ion battery and preparation method |
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Granted publication date: 20091202 Termination date: 20130613 |