CN107331831A - A kind of sijna nano composite material and preparation method thereof - Google Patents
A kind of sijna nano composite material and preparation method thereof Download PDFInfo
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- CN107331831A CN107331831A CN201610271748.4A CN201610271748A CN107331831A CN 107331831 A CN107331831 A CN 107331831A CN 201610271748 A CN201610271748 A CN 201610271748A CN 107331831 A CN107331831 A CN 107331831A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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 invention provides a kind of sijna nano composite material and preparation method thereof, its preparation method, including：（1）Tin-salt solution is slowly added dropwise in certain density aqueous slkali；（2）Transition metal TM salting liquids are slowly dropped into mixed solution, sediment is obtained；（3）Centrifuge and clean sediment, sediment is then added to carbon source organic solution, after stirring, drying；（4）The product of drying is sintered in tube furnace, obtain described nanometer tinbase composite negative pole material, the preparation method safety, operating procedure are simple, the cycle is short, cost is low, composite negative pole material prepared by this method is made up of the compound particle of nanometer tin or tin, alloying, carbon material and nanostructured can alleviate volumetric expansion of the tin during removal lithium embedded, effectively improve circulation and the high rate performance of battery.
Description
Technical field
The present invention relates to lithium ion battery electrochemical field, more particularly to a kind of sijna nano composite material and its preparation side
Method.
Background technology
Continue with World Economics, at high speed develop, gradually deepen the problems such as energy shortage, environmental pollution, ecological degeneration,
Energy supply and demand contradiction, many countries are on energy use efficiency, exploitation regenerative resource and environmental protection is improved
Carried out positive exploration and practice, no matter all will be from the energy or environmental angle, hybrid vehicle and pure power vehicle
Substitute and be preferably selected by the automobile of fossil fuel, lithium ion battery has that voltage is high, specific energy is big, light weight, environment friend
Good the advantages of, the fields such as portable type electronic product and electric tool are had been widely used at present, and be expected to turn into following mixing
One of energy resource supply of power vehicle and pure power vehicle.
The low capacity of the current graphite cathode material of industrialized production（Theoretical specific capacity is 372mAh/g）, it is impossible to it is suitable
Answer current development high-energy, the requirement of high security electrokinetic cell.
Metal tin-based material has high storage lithium ability, is a kind of very promising negative material.
But tin negative pole material has in charge and discharge process that Volume Changes are big, first charge-discharge circulation coulombic efficiency is low, high power
The problems such as rate poor performance.
These problems are solved, are mainly mutually combined by inertia, the approach such as loose structure and nano structural material overcomes gold
Belong to the volumetric expansion of tin, improve the performance of negative pole.
Sn-TM (TM is Cu, Ni, Co) nano composite anode material is by wide coverage, and it is prepared uses electro-deposition more
Method, template, sol-gel process, and these methods yield poorly in the presence of 1,2 preparation process are complicated, and 3 cycles are long, and 4 costs are high, and 5
Whard to control the problems such as.
The content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art, and to provide a kind of sijna nano composite material and its preparation side
Method, this method has 1 yield high, and 2 preparation process are simple, and 3 cycles are short, and 4 costs are low, and 5 the features such as be easily controlled, and for preparing receives
Rice composite negative pole material, solves Volume Changes of the tin as cell negative electrode material in charge and discharge process, improves electrode
Performance.
Realizing the technical scheme of the object of the invention is：
A kind of sijna nano composite material and preparation method thereof, comprises the steps：
1）In the aqueous slkali that tin-salt solution is slowly dropped into finite concentration pH value 9-13；
2）Transition metal is added in TM salting liquids, then mixture is slowly dropped into step 1）In the solution of gained, obtain
Sediment；
3）Centrifugation, cleaning step 2）The sediment of middle acquisition, then sediment is added in carbon source organic solution, stirring is equal
It is even, sediment is dried, presoma is obtained；
4）Presoma is sintered in tube furnace, sijna nano composite material is obtained.
Step 1）In, described pink salt is stannic chloride, stannous chloride or stannous sulfate, and described aqueous slkali is sodium hydroxide
Need to add carbon in one kind or its mixed solution in solution, potassium hydroxide solution, ammoniacal liquor, urea liquid, described aqueous slkali
Material and pH value regulator solution, described carbon material are carbon nanometer bead or/and activated carbon nano particle；Described conditioning agent
For citric acid, ammoniacal liquor and one kind of acetic acid or its mixed solution；
Step 2）In, described transition metal is Cu, Ni or Co；Described TM salting liquids be sulfate, chlorate, nitrate,
It is a kind of in acetate, oxalates；
Described pink salt is with TM salt molar ratios：Sn:TM=1:0.5~2.The ratio of this emergent mixed solution is
What step 1+ steps 2 occurred, it should which where or time are stated；
Step 3）In, described carbon source organic matter is glucose, sucrose or PVP, and described solvent is deionized water or ethanol；
Step 4）In, sintering atmosphere is inert atmosphere, N2/H2Mixed gas or Ar/H2Hydrogen contains in mixed gas, mixed gas
Measure as 5% ~ 10%；Sintering temperature is 200 ~ 500 DEG C；Sintering time is 4 ~ 8 hours；By room temperature be raised to the speed of sintering temperature for 2 ~
10 ℃/min。
Final product prepared by the above method is sijna nano composite material, and its phosphorus content is 0 ~ 40 wt%, this sijna
Nano composite material is made up of the compound particle of nanometer tin or tin, and alloying, carbon material and porous nanometer structure can alleviate tin
Volumetric expansion during removal lithium embedded, effectively improves circulation and the high rate performance of battery.
It is an advantage of the invention that：
1）High with 1 yield, 2 preparation process are simple, and 3 cycles are short, and 4 costs are low, and 5 is safe the features such as being easily controlled, and to be directed to
This 5 points explanation, can just obtain conclusion below.
Operating method is simple, and short preparation period, cost is low, it is possible to achieve large-scale production；
Embodiment
Present invention is further elaborated below by embodiment, but is not limitation of the invention.
Embodiment：
A kind of sijna nano composite material and preparation method thereof, comprises the steps:
1）In the aqueous slkali that tin-salt solution is slowly dropped into finite concentration pH value 9-13；
2）Transition metal is added in TM salting liquids, then mixture is slowly dropped into step 1）In the solution of gained, obtain
Sediment；
3）Centrifugation, cleaning step 2）The sediment of middle acquisition, then sediment is added in carbon source organic solution, stirring is equal
It is even, sediment is dried, presoma is obtained；
4）Presoma is sintered in tube furnace, sijna nano composite material is obtained.
Step 1）In, described pink salt is stannic chloride, stannous chloride or stannous sulfate, and described aqueous slkali is sodium hydroxide
Need to add carbon in one kind or its mixed solution in solution, potassium hydroxide solution, ammoniacal liquor, urea liquid, described aqueous slkali
Material and pH value regulator solution, described carbon material are carbon nanometer bead or/and activated carbon nano particle；Described conditioning agent
For citric acid, ammoniacal liquor and one kind of acetic acid or its mixed solution；
Step 2）In, described transition metal is Cu, Ni or Co；Described TM salting liquids be sulfate, chlorate, nitrate,
It is a kind of in acetate, oxalates；
Described pink salt is with TM salt molar ratios：Sn:TM=1:0.5~2.The ratio of this emergent mixed solution is
What step 1+ steps 2 occurred, it should which where or time are stated；
Step 3）In, described carbon source organic matter is glucose, sucrose or PVP, and described solvent is deionized water or ethanol；
Step 4）In, sintering atmosphere is inert atmosphere, N2/H2Mixed gas or Ar/H2Hydrogen contains in mixed gas, mixed gas
Measure as 5% ~ 10%；Sintering temperature is 200 ~ 500 DEG C；Sintering time is 4 ~ 8 hours；By room temperature be raised to the speed of sintering temperature for 2 ~
10 ℃/min。
Final product prepared by the above method is sijna nano composite material, and its phosphorus content is 0 ~ 40 wt%, this sijna
Nano composite material is made up of the compound particle of nanometer tin or tin, and alloying, carbon material and porous nanometer structure can alleviate tin
Volumetric expansion during removal lithium embedded, effectively improves circulation and the high rate performance of battery.
What this method was provided is used for the tin-based material of negative pole in lithium ion battery, and stanniferous class stores up lithium active material
（Cu6Sn5）And inert material（Cu3Sn）And copper product is all present in micro-nano material, intermediate layer is tin simple substance or tinbase oxygen
Compound, outer layer is copper or gun-metal.
Specifically, example 1.
Prepare nanometer tin-copper composite negative pole material
（1）Sodium hydroxide solution is configured, the use of lemon acid for adjusting pH value is 11, by 50 ml prepared, 0.5 mol/L chlorinations
Stannous solution is added dropwise in sodium hydroxide solution dropwise；
（2）50 mL, 0.5 mol/L copper chloride solutions are taken to be slowly added dropwise into（1）In the mixed solution of step；
（3）After reaction terminates, sediment is centrifuged, washed, vacuum drying obtains presoma；
（4）Presoma is sintered in tube furnace, sintering atmosphere is the mixed gas of hydrogen/argon gas, and sintering temperature is 450
DEG C, heating rate is 3 DEG C/min, and sintering time is 4 hours, naturally cools to room temperature, produces nanometer tin-copper composite negative pole material
Material.
Using tin obtained above-copper composite negative pole material as positive pole, lithium piece is to electrode, 1M LiPF6 EC/DMC
(Vol 1:1) solution is electrolyte, and the diaphragm papers of Celgard 2325 are battery diaphragm, and assembling button half-cell carries out performance survey
Examination.It is 100 mA/g to test charging and discharging currents density, and cut-off charging/discharging voltage is 0.01 ~ 2.0 V.After 100 times circulate, prepare
The capacity of tin-copper composite negative pole material remain 344 mAh/g.
Example 2.
Prepare porous nano tin-copper/carbon compound cathode materials
（1）Weigh a certain amount of Nano carbon balls to be scattered in the sodium hydroxide solution configured, under magnetic agitation effect, by sulphur
Sour stannous solution is slowly dropped into sodium hydroxide solution；
（2）Copper-bath is slowly added dropwise into（1）In the mixed solution of step, after reaction terminates, centrifuge, washing, collect heavy
Starch；
（3）Sediment is added in glucose ethanol solution, ultrasound is uniform, and vacuum drying obtains presoma；
（4）Presoma is sintered in tube furnace, sintering atmosphere is the mixed gas of hydrogen/argon gas, and sintering temperature is 400
DEG C, heating rate is 2 DEG C/min, and sintering time is 5 hours, naturally cools to room temperature, produces porous nano tin-copper/carbon and is combined
Negative material.
It is positive pole by porous nano tin-copper/carbon compound cathode materials obtained above, is assembled into 2032 button half-cells and enters
Row performance test.Test result shows that charging and discharging currents density is under the conditions of 100 mA/g, discharge capacity is 867 mAh/ first
g；After 40 circulations, charging and discharging currents density is under the conditions of 1000 mA/g, discharge capacity remains 267 mAh/g.
Claims (8)
1. a kind of sijna nano composite material and preparation method thereof, it is characterized in that, comprise the steps:
1）In the aqueous slkali that tin-salt solution is slowly dropped into finite concentration pH value 9-13；
2）Transition metal is added in TM salting liquids, then mixture is slowly dropped into step 1）In the solution of gained, obtain
Sediment；
3）Centrifugation, cleaning step 2）The sediment of middle acquisition, then sediment is added in carbon source organic solution, stirring is equal
It is even, sediment is dried, presoma is obtained；
4）Presoma is sintered in tube furnace, sijna nano composite material is obtained.
2. sijna nano composite material according to claim 1 and preparation method thereof, it is characterized in that, step 1）In, it is described
Pink salt is stannic chloride, stannous chloride or stannous sulfate, described aqueous slkali is sodium hydroxide solution, potassium hydroxide solution, ammoniacal liquor,
Addition carbon material and pH value regulator solution, institute are needed in one kind or its mixed solution in urea liquid, described aqueous slkali
The carbon material stated is carbon nanometer bead or/and activated carbon nano particle；Described conditioning agent is the one of citric acid, ammoniacal liquor and acetic acid
Plant or its mixed solution.
3. sijna nano composite material according to claim 1 and preparation method thereof, it is characterized in that, step 2）In, it is described
Transition metal is Cu, Ni or Co；Described TM salting liquids are one in sulfate, chlorate, nitrate, acetate, oxalates
Kind.
4. sijna nano composite material according to claim 1 and preparation method thereof, it is characterized in that, described pink salt and TM salt
Molar ratio is：Sn:TM=1:0.5~2.
5. the ratio of this emergent mixed solution is what step 1+ steps 2 occurred, it should which where or time enter
Row statement.
6. sijna nano composite material according to claim 1 and preparation method thereof, it is characterized in that, step 3）In, it is described
Carbon source organic matter is glucose, sucrose or PVP, and described solvent is deionized water or ethanol.
7. sijna nano composite material according to claim 1 and preparation method thereof, it is characterized in that, step 4）In, sinter gas
Atmosphere is inert atmosphere, N2/H2Mixed gas or Ar/H2Hydrogen content is 5% ~ 10% in mixed gas, mixed gas；Sintering temperature
For 200 ~ 500 DEG C；Sintering time is 4 ~ 8 hours；The speed for being raised to sintering temperature by room temperature is 2 ~ 10 DEG C/min.
8. sijna nano composite material prepared by the preparation method described in claim any one of 1-6, the nano composite anode material
Material includes the one or more of the compound of nanometer tin or nanometer tin.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610271748.4A CN107331831A (en) | 2016-04-28 | 2016-04-28 | A kind of sijna nano composite material and preparation method thereof |
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| CN201610271748.4A CN107331831A (en) | 2016-04-28 | 2016-04-28 | A kind of sijna nano composite material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109148845A (en) * | 2018-08-07 | 2019-01-04 | 欣旺达电子股份有限公司 | The nitrogen-doped carbon negative electrode material and preparation method thereof of nanometer tin modification |
| CN109546130A (en) * | 2018-11-29 | 2019-03-29 | 陕西科技大学 | A kind of method that hydro-thermal calcination method prepares C/Sn/ carbon cloth negative electrode material |
| CN110082406A (en) * | 2019-06-06 | 2019-08-02 | 吉林大学 | One kind being based on SnO2-Co3O4The dimethylbenzene gas sensor and preparation method thereof of hetero-junctions nanostructure sensitive material |
-
2016
- 2016-04-28 CN CN201610271748.4A patent/CN107331831A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109148845A (en) * | 2018-08-07 | 2019-01-04 | 欣旺达电子股份有限公司 | The nitrogen-doped carbon negative electrode material and preparation method thereof of nanometer tin modification |
| CN109148845B (en) * | 2018-08-07 | 2021-03-02 | 欣旺达电子股份有限公司 | Nano-tin-modified nitrogen-doped carbon negative electrode material and preparation method thereof |
| CN109546130A (en) * | 2018-11-29 | 2019-03-29 | 陕西科技大学 | A kind of method that hydro-thermal calcination method prepares C/Sn/ carbon cloth negative electrode material |
| CN110082406A (en) * | 2019-06-06 | 2019-08-02 | 吉林大学 | One kind being based on SnO2-Co3O4The dimethylbenzene gas sensor and preparation method thereof of hetero-junctions nanostructure sensitive material |
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