CN103137956A - Preparation method of nickel-tin alloy powder with porous and globular structures as lithium ion battery negative pole material - Google Patents
Preparation method of nickel-tin alloy powder with porous and globular structures as lithium ion battery negative pole material Download PDFInfo
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- CN103137956A CN103137956A CN2013100901395A CN201310090139A CN103137956A CN 103137956 A CN103137956 A CN 103137956A CN 2013100901395 A CN2013100901395 A CN 2013100901395A CN 201310090139 A CN201310090139 A CN 201310090139A CN 103137956 A CN103137956 A CN 103137956A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of nickel-tin alloy powder with porous and globular structures as a lithium ion battery negative pole material. The nickel-tin powder employs NiSn3 or Ni3Sn8 as the main material doped with a small amount of one of Al, Sb, Zn, Ca, Mg and P, wherein the mass percent of the nickel-tin alloy is 95-98.5% and that of the doped material is 1.5-5%; the preparation method of the composite material comprises the step of: smelting, cutting and carrying out high-temperature spraying on nickel, tin and other metal, and then processing by lye, thus obtaining the nickel-tin alloy powder with porous and globular structures; and when being applied to a lithium ion battery negative pole, the composite material is very high in specific capacity and excellent in cycle performance, the discharge capacity at a current rate of 0.1C is more than 450 mAh/g, the initial charge-discharge efficiency is more than 85%, and the capacity after cycling 50 times is kept to be 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 that current electrokinetic cell is used the huge challenge that 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 that industrialization prospect is arranged very much.The specific discharge capacity of Sn is existing 2 times of left and right with the carbon negative pole, volume and capacity ratio is for now using more than 3 times of carbon negative pole, 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 problems such as irreversible capacity is high, coulombic efficiency is low first, the 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.At first adhere to one deck tin on the copper matrix; 2) preparation plating solution: 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 15～35 ℃ of temperature, pH=8～9, current density is 5～20mA/cm
2, be 0.5～2.5h conduction time, obtains the tin-cobalt alloy material.The tin-cobalt alloy degree of crystallinity that this invention is prepared is high, and serious reunion and surface oxidation be difficult for to occur, and has reduced the irreversible capacity of negative material, and reversible capacity is up to 545mAh/g, circulate still remain on 400mAh/g after 10 times more than.But the major defect of electrodeposition process is that the influencing factor of technique is more, such as the amount of 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 as the substrate as magnetron sputtering of the metal forming of membrane electrode collector, and carry out substrate and clean; (2) regulate sputtering chamber air pressure to 1.0 * 10
-3Pa or more than, then pass into inert gas and adjustable pressure in 0.1～10Pa scope; (3) magnetron sputtering prepares aluminum-tin alloy film, needs to regulate sputtering power in 10W～5kW scope, and the sputter 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 of the 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 efficient is high, no coupling product; The thin-film electrode material uniform crystal particles of preparing is tiny, degree of crystallinity and good mechanical properties.But there is the low shortcoming that reaches the equipment complexity of deposition rate in magnetron sputtering method.
Patent of invention (ZL200610011618.3) adopts the standby a kind of high power capacity Sn-Ni alloy complex lithium ion battery negative material of mechanical ball milling legal system.The oxide of tin, nickel is carried out proportioning in the ratio of Sn and Ni in the alloy complex that generates, then introduce the carbon dust of proper proportion as reducing agent, the mixture that obtains is after mix grinding is even, be placed in mobile inert argon atmosphere and rise to 800-1200 ℃ with the heating rate of 5-30 ℃/minute, be incubated 1-6 hour, then outage, make it cool to room temperature with the furnace.The Sn-Ni lithium ion battery negative material specific capacity of preparing of this invention preparation is high, uniform particles is tiny, and degree of crystallinity is good, stable cycle performance, and reversible capacity is up to 389mAh/g, and specific capacity remains on 97.9% after 12 circulations.Advantage be: the shortcoming of the method is that Mechanical Milling Process easily introduces impurity, and ball milling product specific area is large, and easily oxidation causes lithium to form stable oxide and cause irreversible capacity loss in telescopiny.
Summary of the invention
The object of the invention is to provide the lithium ion battery negative material nickeltin powder preparation method of a kind of porous, chondritic, overcomes the defective 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 that the lithium ion battery negative material nickel tin material that provides is with NiSn
3Or Ni
3Sn
8Be main, a small amount of Al that adulterates, Sb, Zb, Ca, Mg, P; Prepare the nickeltin ingot through smelting process; Then obtain spherical nickeltin powder by the high-temperature injection stove, then adopt alkali lye to process, obtain the nickeltin powder of porous, chondritic.The present invention is achieved by the following technical solutions:
The lithium ion battery negative material nickeltin powder preparation method of a kind of porous, chondritic, it is characterized in that: the nickel tin powder is with NiSn
3Or Ni
3Sn
8Be main, a small amount of Al that adulterates, Sb, Zn, Ca, Mg, a kind of in P; Wherein, nickeltin accounts for 95～98.5mol%, and dopant is 1.5～5mol%; The preparation method of nickel tin material comprises the steps:
1), the nickel of the certain molal quantity of weighing, tin and dopant; Argon shield adopts smelting process to prepare the nickeltin ingot;
2), with the cutting of the nickeltin ingot of step (1), obtain the primary alloy piece;
3), the nickeltin piece of step (2) is put into the high-temperature injection stove, argon shield is heated to 1500～1750 ℃, melting 3～5 hours; High-pressure injection, condensation obtain the spherical nickeltin powder of 5～40um;
4), with the product that step (3) obtains, immerse excessive 10～40wt% aqueous slkali 2～24h; 80～150 ℃ of reaction temperatures, the product centrifugation is also washed 2～3 times with distilled water;
5), product that step (4) is obtained, at 60～100 ℃ of vacuumize 5～10h, obtain 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 10um, 15um, a kind of in 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 a kind of or two kinds;
The lithium ion battery negative material nickeltin powder preparation method of a kind of porous provided by the invention, chondritic, the preparation method compares with other nickel tin material, has following advantage:
1) technique of the present invention is simple, easy to operate, is conducive to suitability for industrialized production.
2) prepared lithium ion battery negative material nickeltin powder, 0.1C discharge capacity are greater than 450mAh/g, and first charge-discharge efficiency keeps more than 90% greater than 85%, 50 circulation volume.
Embodiment one,
Embodiment
For further understanding summary of the invention of the present invention, Characteristic, hereby lift following examples, and coordinate accompanying drawing to be described in detail as follows:
Embodiment 1
The lithium ion battery negative material nickeltin powder preparation method of a kind of 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;
1), nickel, tin and the dopant of the certain molal quantity of weighing its concrete steps are:; Argon shield adopts smelting process to prepare the nickeltin ingot; 2), with the cutting of the nickeltin ingot of step (1), obtain the primary alloy piece; 3), the nickeltin piece of step (2) is put into the high-temperature injection stove, adopting diameter is 15um injection mold spray-hole, and argon shield is heated to 1650 ℃, melting 5 hours; High-pressure injection, condensation obtain the spherical nickeltin powder about 15um; 4), with the nickeltin powder that step (3) obtains, immerse excessive 40wt% sodium hydroxide solution 10h; 80 ℃ of reaction temperatures, the product centrifugation is also washed 2～3 times with distilled water; 5), product that step (4) is obtained, at 100 ℃ of vacuumize 5h, obtain the nickeltin powder of porous, chondritic.
The preparation and property test of electrode; Composite material, acetylene black and PVDF among NMPs are mixed in mass ratio at 90: 5: 5, be coated in and be electrode film on Copper Foil, metal lithium sheet is to electrode, CELGARD2400 is barrier film, the LiPF6/EC+DMCWEI of 1mol/L is electrolyte, be assembled into button cell in being full of the Ar glove box, adopting the Land battery test system to carry out the constant current charge-discharge test.The charging/discharging voltage scope is 2.0～0.01V, and current density is 30mA/g (0.1C). electro-chemical test sees Table one.
Embodiment 2
With embodiment 1 operation, system 5 is identical with system 2 Composition Designs, changes lithium ion battery negative material nickeltin powder preparation method.Its step is as follows: 1) weighing nickel metal 1mol, tin metal 3mol, zinc metal 0.03mol; Argon shield adopts smelting process to prepare the nickeltin ingot; 2), with the cutting of the nickeltin ingot of step (1), obtain the primary alloy piece; 3), the nickeltin piece of step (2) is put into the high-temperature injection stove, adopting diameter is 10um injection mold spray-hole, and argon shield is heated to 1600 ℃, melting 3 hours; High-pressure injection, condensation obtain the spherical nickeltin powder about 10um; 4), with the nickeltin powder that step (3) obtains, immerse excessive 30wt% aqua calcis 10h; 100 ℃ of reaction temperatures, the product centrifugation is also washed 2～3 times with distilled water; 5), product that step (4) is obtained, at 60 ℃ of vacuumize 5h, obtain the nickeltin powder of porous, chondritic.
The preparation and property test of electrode is as embodiment 1; Electro-chemical test sees Table one.
Embodiment 3
With embodiment 1 operation,
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) a certain amount of nickel metal of weighing, tin metal and doping metals; Argon shield adopts smelting process to prepare the nickeltin ingot; 2), with the cutting of the nickeltin ingot of step (1), obtain the primary alloy piece; 3), the nickeltin piece of step (2) is put into the high-temperature injection stove, adopting diameter is 20um injection mold spray-hole, and argon shield is heated to 1750 ℃, melting 4 hours; High-pressure injection, condensation obtain the spherical nickeltin powder about 20um; 4), with the nickeltin powder that step (3) obtains, immerse excessive 20wt% potassium hydroxide solution 10h; 150 ℃ of reaction temperatures, the product centrifugation is also washed 2～3 times with distilled water; 5), product that step (4) is obtained, at 70 ℃ of vacuumize 5h, obtain the nickeltin powder of porous, chondritic.
The preparation and property test of electrode is as embodiment 1; Electro-chemical test sees Table one.
Embodiment 4
With embodiment 3 operations,
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) weighing nickel metal 3mol, tin metal 8mol, magnesium metal 0.05mol; Argon shield adopts smelting process to prepare the nickeltin ingot; 2), with the cutting of the nickeltin ingot of step (1), obtain the primary alloy piece; 3), the nickeltin piece of step (2) is put into the high-temperature injection stove, adopting diameter is 10um injection mold spray-hole, and argon shield is heated to 1550 ℃, melting 5 hours; High-pressure injection, condensation obtain the spherical nickeltin powder about 10um; 4), with the nickeltin powder that step (3) obtains, immerse excessive 20wt% potassium hydroxide and potassium hydroxide solution 5h; 120 ℃ of reaction temperatures, the product centrifugation is also washed 2～3 times with distilled water; 5), product that step (4) is obtained, at 800 ℃ of vacuumize 5h, obtain the nickeltin powder of porous, chondritic.
The preparation and property test of electrode is as embodiment 1; Electro-chemical test sees Table one.
Table one: the chemical property of the lithium ion battery negative material nickeltin powder of porous, chondritic
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.
Claims (1)
1. the lithium ion battery negative material nickeltin powder preparation method of a porous, chondritic, it is characterized in that: the nickel tin powder is with NiSn
3Or Ni
3Sn
8Be main, a small amount of Al that adulterates, Sb, Zn, Ca, Mg, a kind of in P; Wherein, nickeltin accounts for 95～98.5%, and dopant is 1.5～5%; The preparation method of nickel tin material comprises the steps:
1), the nickel of the certain molal quantity of weighing, tin and dopant; Argon shield adopts smelting process to prepare the nickeltin ingot;
2), with the cutting of the nickeltin ingot of step (1), obtain the primary alloy piece;
3), the nickeltin piece of step (2) is put into the high-temperature injection stove, argon shield is heated to 1500～1750 ℃, 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 10um, 15um, a kind of in 20um;
4), with the product that step (3) obtains, immerse excessive 10～40wt% aqueous slkali 2～24h; 80～150 ℃ of reaction temperatures, the product centrifugation is also washed 2～3 times with distilled water;
Wherein, alkali is NaOH, KOH, Ca (OH)
2, Ba (OH)
2In a kind of or two kinds;
5), product that step (4) is obtained, at 60～100 ℃ of vacuumize 5～10h, obtain the nickeltin powder of porous, chondritic.
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| CN201310090139.5A CN103137956B (en) | 2013-03-15 | 2013-03-15 | The lithium ion battery negative material nickeltin powder preparation method of a kind of porous, chondritic |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104167538A (en) * | 2014-07-29 | 2014-11-26 | 中国计量学院 | Preparation method of Li4Ti5O12/NiSn composite material |
| 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 |
| CN108807850A (en) * | 2017-05-01 | 2018-11-13 | 深圳格林德能源有限公司 | A kind of novel alloy electrode and its sodium-ion battery |
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| 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 |
| WO2012086835A1 (en) * | 2010-12-24 | 2012-06-28 | 山陽特殊製鋼株式会社 | Sn alloy powder for negative electrodes of lithium ion batteries, and method for producing same |
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2013
- 2013-03-15 CN CN201310090139.5A patent/CN103137956B/en not_active Expired - Fee Related
Patent Citations (4)
| 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 |
| WO2012086835A1 (en) * | 2010-12-24 | 2012-06-28 | 山陽特殊製鋼株式会社 | Sn alloy powder for negative electrodes of lithium ion batteries, and method for producing same |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104167538A (en) * | 2014-07-29 | 2014-11-26 | 中国计量学院 | Preparation method of Li4Ti5O12/NiSn composite material |
| 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 |
| CN108807850A (en) * | 2017-05-01 | 2018-11-13 | 深圳格林德能源有限公司 | A kind of novel alloy electrode and its sodium-ion battery |
| 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 |
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