CN103137956B - The lithium ion battery negative material nickeltin powder preparation method of a kind of porous, chondritic - Google Patents
The lithium ion battery negative material nickeltin powder preparation method of a kind of porous, chondritic Download PDFInfo
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- CN103137956B CN103137956B CN201310090139.5A CN201310090139A CN103137956B CN 103137956 B CN103137956 B CN 103137956B CN 201310090139 A CN201310090139 A CN 201310090139A CN 103137956 B CN103137956 B CN 103137956B
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- 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 relates to the lithium ion battery negative material nickeltin powder preparation method of a kind of porous, chondritic.Nickel tin powder is with NiSn
3or Ni
3sn
8be main, adulterate a small amount of Al, the one in Sb, Zn, Ca, Mg, P; Wherein, nickeltin accounts for 95 ~ 98.5%, and dopant is 1.5 ~ 5%; The preparation method of this composite material comprises: the metals such as nickel tin are through melting, cutting, high-temperature injection, and base extraction obtains the nickeltin powder of porous, chondritic; When this composite material is used for lithium ion battery negative, have very high specific capacity and excellent cycle performance: 0.1C discharge capacity is greater than 450mAh/g, and first charge-discharge efficiency is greater than 85%, after 50 circulations, capacity remains on more than 90%.
Description
Technical field
The present invention relates to a kind of preparation method of battery electrode material, specifically relate to the lithium ion battery negative material nickeltin powder preparation method of a kind of porous, chondritic.
Background technology
Development high security, high-energy, low cost, extended-life lithium ion battery are the huge challenges that current power battery applications faces.The performance of battery depends primarily on the performance of both positive and negative polarity electrode material.Sn base alloy anode has high-energy and security feature, is a kind of height ratio capacity lithium ion battery negative material having very much industrialization prospect.The specific discharge capacity of Sn is about 2 times of existing Carbon anode, volume and capacity ratio is more than 3 times of existing Carbon anode, its removal lithium embedded current potential has relatively high fail safe a little more than carbon electrode, but, in Sn base alloy removal lithium embedded process, change in volume greatly, first and then cause cycle performance unstable, and the problem such as irreversible capacity is high first, coulombic efficiency is low, scientific research personnel has done a large amount of trials and exploration.
Patent of invention (number of patent application: 200710057608.8) adopt electro-deposition method to prepare luxuriant shape and spherical tin-cobalt alloy negative electrode material.First on Copper substrate, one deck tin is adhered to; 2) plating solution is prepared: 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; Pass through electro-deposition method: control temperature 15 ~ 35 DEG C, pH=8 ~ 9, current density is 5 ~ 20mA/cm
2, conduction time is 0.5 ~ 2.5h, obtains tin-cobalt alloy material.The tin-cobalt alloy degree of crystallinity that this invention is prepared is high, and serious reunion and surface oxidation not easily occur, and decrease the irreversible capacity of negative material, reversible capacity is up to 545mAh/g, circulates after 10 times and still remains on more than 400mAh/g.But the major defect of electrodeposition process is that the influencing factor of technique is more, the amount of such as current density, concentration of electrolyte, additive and temperature etc.
Patented invention (number of patent application: 200810028685.5) provide a kind of magnetron sputtering method to prepare aluminum-tin alloy film for lithium ionic cell negative electrode.(1) select metal forming as membrane electrode collector as the substrate of magnetron sputtering, and carry out substrate cleaning; (2) sputtering chamber air pressure to 1.0 × 10 are regulated
-3pa or more, then pass into inert gas and adjustable pressure in 0.1 ~ 10Pa scope; (3) magnetron sputtering prepares aluminum-tin alloy film, and sputtering power need be regulated in 10W ~ 5kW scope, and sputtering type is magnetically controlled DC sputtering or rf magnetron sputtering, and the sputtering sedimentation time was 10 ~ 60 minutes scopes.Aluminum-tin alloy film for lithium ionic cell negative electrode is made up of solid solution alloy material mock silver, and in alloy, the content of tin is 25 ~ 75%, and all the other are aluminium.Operating procedure of the present invention is simple, and cost is low, and efficiency is high, no coupling product; The thin-film electrode material uniform crystal particles prepared is tiny, degree of crystallinity and good mechanical properties.But there is the shortcoming that deposition rate is low and equipment is complicated in magnetron sputtering method.
Patent of invention (ZL 200610011618.3) adopts mechanical attrition method to prepare a kind of high power capacity Sn-Ni alloy complex lithium ion battery negative material.The oxide of tin, nickel is carried out proportioning in the ratio of Sn and Ni in generated alloy complex, then the carbon dust of proper proportion is introduced as reducing agent, the mixture obtained is after mix grinding is even, the inert argon atmosphere being placed in flowing rises to 800-1200 DEG C with the heating rate of 5-30 DEG C/min, insulation 1-6 hour, then power-off, makes it cool to room temperature with the furnace.The Sn-Ni specific capacity of negative electrode material of lithium ion battery that prepared by this invention prepare is high, uniform particles is tiny, and degree of crystallinity is good, stable cycle performance, and reversible capacity is up to 389mAh/g, and after 12 circulations, specific capacity remains on 97.9%.Advantage be: the shortcoming of the method is that Mechanical Milling Process easily introduces impurity, and ball milling product specific area is large, oxidizable, causes lithium form stable oxide in telescopiny and cause irreversible capacity loss.
Summary of the invention
The object of the invention is the lithium ion battery negative material nickeltin powder preparation method providing a kind of porous, chondritic, overcomes the defect of existing technology of preparing, improves cycle life and the specific capacity of nickel tin material.For achieving the above object, technical scheme of the present invention is, the lithium ion battery negative material nickel tin material provided, with NiSn
3or Ni
3sn
8be main, adulterate a small amount of Al, Sb, Zb, Ca, Mg, P; Nickeltin ingot is prepared through smelting process; Then obtain spherical nickeltin powder by high-temperature injection stove, then adopt base extraction, obtain the nickeltin powder of porous, chondritic.The present invention is achieved by the following technical solutions:
A lithium ion battery negative material nickeltin powder preparation method for porous, chondritic, is characterized in that: nickel tin powder is with NiSn
3or Ni
3sn
8be main, adulterate a small amount of Al, the one in Sb, Zn, Ca, Mg, P; Wherein, nickeltin accounts for 95 ~ 98.5mol%, and dopant is 1.5 ~ 5mol%; The preparation method of nickeltin powder comprises the steps:
1) nickel of certain molal quantity, tin and dopant, is weighed; Argon shield, adopts smelting process to prepare nickeltin ingot;
2), by the nickeltin ingot of step (1) cut, obtain primary alloy block;
3), by the nickeltin block of step (2) put into high-temperature injection stove, argon shield, be heated to 1500 ~ 1750 DEG C, melting 3 ~ 5 hours; High-pressure injection, condensation, obtain the spherical nickeltin powder of 5 ~ 40um;
4) product, by step (3) obtained, immerses excessive 10 ~ 40wt% aqueous slkali 2 ~ 24h; Reaction temperature 80 ~ 150 DEG C, product centrifugation is also washed 2 ~ 3 times with distilled water;
5) product, by step (4) obtained, at 60 ~ 100 DEG C of vacuumize 5 ~ 10h, obtains the nickeltin powder of porous, chondritic.
The lithium ion battery negative material nickeltin powder preparation method of described a kind of porous, chondritic, wherein, described injection mold nozzle inside diameter is the one in 10um, 15um, 20um;
The lithium ion battery negative material nickeltin powder preparation method of described a kind of porous, chondritic, wherein, described alkali is NaOH, KOH, Ca (OH)
2, Ba (OH)
2in one or two kinds;
The lithium ion battery negative material nickeltin powder preparation method of a kind of porous provided by the invention, chondritic, compared with other nickel tin material preparation method, tool has the following advantages:
1) present invention process is simple, easy to operate, is conducive to suitability for industrialized production.
2) the lithium ion battery negative material nickeltin powder prepared by, 0.1C discharge capacity is greater than 450mAh/g, and first charge-discharge efficiency is greater than 85%, and 50 times circulation volume keeps more than 90%.
Embodiment one,
Embodiment
For summary of the invention of the present invention, Characteristic can be understood further, hereby lift following examples, and coordinate accompanying drawing to be described in detail as follows:
Embodiment 1
A lithium ion battery negative material nickeltin powder preparation method for porous, chondritic, Composition Design is:
System 1: nickel metal 1mol, tin metal 3mol, aluminum metal 0.03mol;
System 2: nickel metal 1mol, tin metal 3mol, zinc metal 0.03mol;
System 3: nickel metal 1mol, tin metal 3mol, calcium metal 0.03mol;
System 4: nickel metal 1mol, tin metal 3mol, antimony metal 0.03mol;
Its concrete steps are: 1), weigh the nickel of certain molal quantity, tin and dopant; Argon shield, adopts smelting process to prepare nickeltin ingot; 2), by the nickeltin ingot of step (1) cut, obtain primary alloy block; 3), by the nickeltin block of step (2) put into high-temperature injection stove, adopt diameter to be 15um injection mold spray-hole, argon shield, is heated to 1650 DEG C, melting 5 hours; High-pressure injection, condensation, obtain the spherical nickeltin powder of about 15um; 4) the nickeltin powder, by step (3) obtained, immerses excessive 40wt% sodium hydroxide solution 10h; Reaction temperature 80 DEG C, product centrifugation is also washed 2 ~ 3 times with distilled water; 5) product, by step (4) obtained, at 100 DEG C of vacuumize 5h, obtains the nickeltin powder of porous, chondritic.
The preparation and property test of electrode; Composite material, acetylene black and PVDF among NMPs to be mixed in mass ratio at 90: 5: 5, be coated on Copper Foil is electrode film, metal lithium sheet is to electrode, CELGARD 2400 is barrier film, the LiPF6/EC+DMCWEI of 1mol/L is electrolyte, be assembled into button cell being full of in Ar glove box, adopt Land battery test system to carry out constant current charge-discharge test.Charging/discharging voltage scope is 2.0 ~ 0.01V, and current density is 30mA/g (0.1C). electro-chemical test is in table one.
Embodiment 2
Operate with embodiment 1, system 5 is identical with system 2 Composition Design, changes lithium ion battery negative material nickeltin powder preparation method.Its step is as follows: 1) weigh nickel metal 1mol, tin metal 3mol, zinc metal 0.03mol; Argon shield, adopts smelting process to prepare nickeltin ingot; 2), by the nickeltin ingot of step (1) cut, obtain primary alloy block; 3), by the nickeltin block of step (2) put into high-temperature injection stove, adopt diameter to be 10um injection mold spray-hole, argon shield, is heated to 1600 DEG C, melting 3 hours; High-pressure injection, condensation, obtain the spherical nickeltin powder of about 10um; 4) the nickeltin powder, by step (3) obtained, immerses excessive 30wt% aqua calcis 10h; Reaction temperature 100 DEG C, product centrifugation is also washed 2 ~ 3 times with distilled water; 5) product, by step (4) obtained, at 60 DEG C of vacuumize 5h, obtains the nickeltin powder of porous, chondritic.
The preparation and property test of electrode is as embodiment 1; Electro-chemical test is in table one.
Embodiment 3
Operate with embodiment 1,
System 6: nickel metal 3mol, tin metal 8mol, P elements 0.04mol;
System 7: nickel metal 3mol, tin metal 8mol, magnesium metal 0.04mol;
System 8: nickel metal 3mol, tin metal 8mol, calcium metal 0.04mol;
Change lithium ion battery negative material nickeltin powder preparation method.Its step is as follows: 1) weigh a certain amount of nickel metal, tin metal and doping metals; Argon shield, adopts smelting process to prepare nickeltin ingot; 2), by the nickeltin ingot of step (1) cut, obtain primary alloy block; 3), by the nickeltin block of step (2) put into high-temperature injection stove, adopt diameter to be 20um injection mold spray-hole, argon shield, is heated to 1750 DEG C, melting 4 hours; High-pressure injection, condensation, obtain the spherical nickeltin powder of about 20um; 4) the nickeltin powder, by step (3) obtained, immerses excessive 20wt% potassium hydroxide solution 10h; Reaction temperature 150 DEG C, product centrifugation is also washed 2 ~ 3 times with distilled water; 5) product, by step (4) obtained, at 70 DEG C of vacuumize 5h, obtains the nickeltin powder of porous, chondritic.
The preparation and property test of electrode is as embodiment 1; Electro-chemical test is in table one.
Embodiment 4
Operate with embodiment 3,
System 9: nickel metal 3mol, tin metal 8mol, magnesium metal 0.05mol; Change lithium ion battery negative material nickeltin powder preparation method.Its step is as follows: 1) weigh nickel metal 3mol, tin metal 8mol, magnesium metal 0.05mol; Argon shield, adopts smelting process to prepare nickeltin ingot; 2), by the nickeltin ingot of step (1) cut, obtain primary alloy block; 3), by the nickeltin block of step (2) put into high-temperature injection stove, adopt diameter to be 10um injection mold spray-hole, argon shield, is heated to 1550 DEG C, melting 5 hours; High-pressure injection, condensation, obtain the spherical nickeltin powder of about 10um; 4) the nickeltin powder, by step (3) obtained, immerses excessive 20wt% potassium hydroxide and potassium hydroxide solution 5h; Reaction temperature 120 DEG C, product centrifugation is also washed 2 ~ 3 times with distilled water; 5) product, by step (4) obtained, at 800 DEG C of vacuumize 5h, obtains the nickeltin powder of porous, chondritic.
The preparation and property test of electrode is as embodiment 1; Electro-chemical test is in table one.
Table one: the chemical property of the lithium ion battery negative material nickeltin powder of porous, chondritic
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (1)
1. a lithium ion battery negative material nickeltin powder preparation method for porous, chondritic, is characterized in that: nickeltin powder is with NiSn
3or Ni
3sn
8be main, adulterate a small amount of Al, the one in Sb, Zn, Ca, Mg, P; Wherein, nickeltin accounts for 95 ~ 98.5mol%, and dopant is 1.5 ~ 5mol%; The preparation method of nickeltin powder comprises the steps:
1) nickel of certain molal quantity, tin and dopant, is weighed; Argon shield, adopts smelting process to prepare nickeltin ingot;
2), by the nickeltin ingot of step (1) cut, obtain primary alloy block;
3), by the nickeltin block of step (2) put into high-temperature injection stove, argon shield, be heated to 1500 ~ 1750 DEG C, melting 3 ~ 5 hours; High-pressure injection, condensation, obtain the spherical nickeltin powder of 5 ~ 40um;
Wherein, the nozzle inside diameter of injection mold is the one in 10um, 15um, 20um;
4) product, by step (3) obtained, immerses excessive 10 ~ 40wt% aqueous slkali 2 ~ 24h; Reaction temperature 80 ~ 150 DEG C, product centrifugation is also washed 2 ~ 3 times with distilled water;
Wherein, alkali is NaOH, KOH, Ca (OH)
2, Ba (OH)
2in one or two kinds;
5) product, by step (4) obtained, at 60 ~ 100 DEG C of vacuumize 5 ~ 10h, obtains the nickeltin powder of porous, chondritic.
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| CN104167538B (en) * | 2014-07-29 | 2016-05-18 | 中国计量学院 | A kind of Li4Ti5O12The preparation method of/NiSn composite |
| CN108400289A (en) * | 2017-02-07 | 2018-08-14 | 万向二三股份公司 | A kind of carbon coating tin base alloy anode material and preparation method thereof |
| CN108807850B (en) * | 2017-05-01 | 2021-08-27 | 深圳格林德能源集团有限公司 | Electrode and sodium ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101071851A (en) * | 2007-06-13 | 2007-11-14 | 天津大学 | Tin-cobalt alloy negative electrode material for lithium ion cell and its preparing method |
| CN100446308C (en) * | 2006-06-27 | 2008-12-24 | 福建师范大学 | Stannum-copper alloy composite oxide membrane negative electrode material and use in battery |
| CN102136567A (en) * | 2011-02-14 | 2011-07-27 | 山东建筑大学 | Preparing method of tin-nickel-carbon composite cathode material of lithium ion battery |
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| JP5594731B2 (en) * | 2010-12-24 | 2014-09-24 | 山陽特殊製鋼株式会社 | Sn alloy powder for negative electrode of lithium ion battery and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100446308C (en) * | 2006-06-27 | 2008-12-24 | 福建师范大学 | Stannum-copper alloy composite oxide membrane negative electrode material and use in battery |
| CN101071851A (en) * | 2007-06-13 | 2007-11-14 | 天津大学 | Tin-cobalt alloy negative electrode material for lithium ion cell and its preparing method |
| CN102136567A (en) * | 2011-02-14 | 2011-07-27 | 山东建筑大学 | Preparing method of tin-nickel-carbon composite cathode material of lithium ion battery |
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